Marine heavy fuel oil composition

Abstract

To provide a marine heavy fuel-oil composition.SOLUTION: There is provided a process of decreasing an environmental pollutant present in a raw material of marine heavy fuel oil (raw material) complying with ISO 8217. The process includes: mixing a specified amount of the raw material with a specified amount of an activated gas mixture to obtain a raw material mixture; allowing the raw material mixture to contact at least one kind of catalyst to prepare a process mixture from the raw material mixture; separating a marine heavy fuel oil product (product), i.e., a liquid component of the process mixture, from a gas component of the process mixture and a byproduct hydrocarbon; and discharging the product. The product complies with ISO standard as marine residual fuel oil with its maximum sulfur content being in a range of 0.05 to 0.50 wt.%. The product can be used as low sulfur or super low sulfur marine heavy fuel oil complying with ISO standard or its blend stock. There is also disclosed a device for practicing the process.SELECTED DRAWING: Figure 1

Description

[Background technology]

[0001] There are two types of marine fuel oil: distillate-based marine fuel oil and residue-based marine fuel oil. Distillate-based marine fuel, also known as marine light oil (MGO) or marine diesel oil (MDO), consists of petroleum fractions separated from crude oil during the distillation process at refineries. Light oil (also known as diesel fuel) has a boiling point range and viscosity that differs between kerosene and C. 10-19 It is a petroleum distillate that is an intermediate between diesel and lubricating oils containing a mixture of hydrocarbons. Diesel fuel is used for heating homes and in heavy machinery such as cranes, bulldozers, generators, bobcats, tractors, and combine harvesters. Generally, by maximizing the recovery of diesel fuel from residual oil, refiners can use their raw materials most economically because they can break down diesel fuel into higher-value gasoline and distillates. Diesel oil is very similar to diesel fuel, and diesel is primarily C 10-19 It contains a mixture of hydrocarbons, consisting of approximately 64% aliphatic hydrocarbons, 1-2% olefinic hydrocarbons, and 35% aromatic hydrocarbons. Marine diesel may contain up to 15% residue process stream and, in some cases, up to 5% by volume of polycyclic aromatic hydrocarbons (asphaltenes). Diesel fuel is mainly used as a fuel for land transport or as a blend component with kerosene in aviation jet fuel.

[0002] Residue oil-based fuels or heavy marine fuel oils (HMFOs) consist of a mixture of process residue oils, which are fractions that do not boil or evaporate even under reduced pressure, and have an asphaltene content of 3-20% by weight (wt%). Asphaltenes are large, complex polycyclic hydrocarbons that tend to form complex, waxy precipitates. Asphaltenes are notoriously difficult to redissolve once precipitated, and are known as fuel tank sludge in the shipping and ship bunker fuel supply industries.

[0003] Large ocean-going vessels have relied on HMFO for over 50 years to power their large two-stroke diesel engines. HMFO is a blend of aromatic compounds, distillates, and residues produced during the crude oil refining process. Typical streams included in the composition of HMFO include atmospheric bottom oil (i.e., atmospheric residue), vacuum bottom oil (i.e., vacuum residue), visbreaker residue, light FCC cycle oil (LCO), heavy FCC cycle oil (HCO) (also known as FCC bottom), FCC slurry oil, heavy diesel and delayed cracker oil (DCO), polycyclic aromatic hydrocarbons, recycled land transport motor oil, and small amounts (less than 20 vol%) of cutter oil, kerosene, or diesel to achieve the desired viscosity. The aromatic content of HMFO is higher than that of the marine distillate fuels mentioned above. The composition of HMFO is complex and varies depending on the crude oil source and the refining process used to extract the maximum value from the crude oil barrels. Mixtures of multiple components are generally viscous, high in sulfur and metals, and high in asphaltenes. For this reason, HMFOs are one of the refining products that have a lower value per barrel than the crude oil raw material itself.

[0004] According to industry statistics, approximately 90% of HMFO sold contains 3.5% by weight of sulfur. With an estimated global consumption of approximately 300 million tons of HMFO per year, the annual sulfur dioxide production by the shipping industry is estimated to exceed 21 million tons. Emissions from HMFO combustion on ships contribute significantly to both global and local air pollution.

[0005] MARPOL (International Convention for the Prevention of Pollution from Ships), enforced by the International Maritime Organization (IMO), was established to prevent pollution from ships. In 1997, a new annex was added to MARPOL: Annex VI, which outlines the rules for preventing air pollution from ships, specifically regarding the minimization of atmospheric emissions from ships (SOx, NOx, ODS, VOCs) and their contribution to air pollution. A revised version of Annex VI, which imposes stricter emission limits, was adopted in October 2008 and came into effect on July 1, 2010 (hereinafter referred to as Annex VI (revised version) or simply Annex VI).

[0006] MARPOL Annex VI (Revised) establishes a series of stringent emission restrictions for ship operations in designated Emission Control Areas (ECAs). The ECAs under MARPOL Annex VI (Revised) are: i) the Baltic Sea (as defined in MARPOL Annex I): SOx only; ii) the North Sea (as defined in MARPOL Annex V): SOx only; iii) North America (as defined in Appendix VII of MARPOL Annex VI): SOx, NOx, and PM; iv) the US Caribbean (as defined in Appendix VII of MARPOL Annex VI): SOx, NOx, and PM.

[0007] Annex VI (Revised) was codified in the United States under the Ship Pollution Prevention Act (APPS). Under the authority of APPS, the U.S. Environmental Protection Agency (EPA), in consultation with the U.S. Coast Guard (USCG), issued a rule incorporating the full text of Annex VI (Revised) of MARPOL. See 40C.FR§1043.100(a)(1). On August 1, 2012, the maximum sulfur content of all marine fuel oils used on vessels operating in U.S. waters / ECA could not exceed 1.00 wt% (10,000 ppm), and on January 1, 2015, the maximum sulfur content of all marine fuel oils used in the North American ECA was reduced to 0.10 wt% (1,000 ppm). Upon entry into force, the U.S. government indicated that ship operators must be well-prepared for the 0.10 wt% (1,000 ppm) U.S. ECA marine fuel oil sulfur standard. To enhance compliance, the EPA and USCG have refused to consider the cost of compliant low-sulfur fuel oil as a valid reason for claiming that compliant fuel oil could not be purchased. Despite very strong economic incentives to meet the shipping industry's demand for low-sulfur HMFO over the past five years, a technically viable solution has not materialized. There is a continuing and urgent need for processes and methods to produce low-sulfur HMFO that meets MARPOL Annex VI emission requirements.

[0008] For the purposes of the ECA, all ocean-going vessels operating both inside and outside the ECA must operate with different marine fuel oils to comply with the respective restrictions and achieve maximum economic efficiency. In such cases, the vessel must completely switch to the use of ECA-compliant marine fuel oil before entering the ECA, and furthermore, documented procedures on board should be followed on how to do so. Similarly, the switch back from ECA-compliant fuel oil to the use of HMFO should not be initiated until after leaving the ECA. For each switch, the amount of ECA-compliant fuel oil on board must be recorded, along with the date, time, and position of the vessel when the switch is completed before entering the area or initiated after leaving it. These records should be kept in the ship's logbook as specified by the ship's flag state, and unless otherwise specified, the records will be kept, for example, in the ship's Annex I fuel logbook.

[0009] Furthermore, Annex VI (revised) imposes global restrictions on the emission of sulfur oxides and nitrogen oxides and particulate matter from ship exhausts, and prohibits the intentional emission of ozone-depleting substances such as hydrochlorofluorocarbons. Under the revised MARPOL Annex VI, the global sulfur limit for HMFO was lowered to 3.50 wt% and came into effect on January 1, 2012, and has since been further lowered to 0.50 wt% and will come into effect on January 1, 2020. This rule is an issue that has been debated extensively in both the shipping and marine fuel supply industries. Under the global restrictions, all ships must use HMFO with a sulfur content of 0.50 wt% or less. The IMO has repeatedly indicated to the shipping industry that compliance with the 0.50 wt% sulfur limit for HMFO will take effect on January 1, 2020, regardless of whether compliant fuel is available or the price of compliant fuel, and that the IMO expects the fuel oil market to address this requirement. Despite very strong economic incentives to meet the international shipping industry's demand for low-sulfur HMFOs, a technically viable solution has not yet been realized. There is a continuing and urgent need for processes and methods to produce low-sulfur HMFOs that comply with MARPOL Annex VI emission requirements.

[0010] IMO Rule 14 specifies both the limits and means to be followed. These can be divided into methods called primary (where the generation of pollutants is avoided) or secondary (where pollutants are generated, but removed before the exhaust gas stream is discharged into the atmosphere). There are no guidelines whatsoever for primary methods (which would include, for example, onboard blending of liquid fuel oil or the use of dual fuel (gaseous / liquid)). For secondary control methods, guidelines for exhaust gas purification systems (MEPC.184(59)) have been adopted. If such equipment is used and the system is certified, there will be no other restrictions on the sulfur content of the fuel oil loaded. For many technical and economic reasons, secondary control methods have been rejected by major shipping companies and are not widely adopted in the shipping industry. The use of secondary control methods is not considered a practical solution by the shipping industry.

[0011] Primary Control Measures: Concerns about compliance with MARPOL requirements have focused on primary control measures, such as reducing sulfur concentrations in marine fuel components before combustion by replacing HMFO with alternative fuels. However, switching from HMFO to alternative fuels presents various problems for ship operators, many of which remain misunderstood by both the shipping and refining industries. Due to the potential risks to the ship's propulsion system (i.e., fuel system, engine, etc.) when ships switch fuels, the conversion process must be carried out safely and efficiently to avoid technical problems. However, it is economically and technically difficult for each alternative fuel to be adapted to the shipping infrastructure and fuel supply systems that the shipping industry has used for decades and which are based on HMFO.

[0012] LNG: The most common primary control measure in the shipping industry is the adoption of LNG as a supplemental fuel to primary fuel or HMFO. The number of ships using liquefied natural gas (LNG) as primary fuel is increasing. When natural gas is used as marine fuel in combustion turbines and diesel engines, sulfur oxide emissions are negligible. The benefits of natural gas were recognized in the IMO's development of the International Guidance for Ships Using Gas and Low Flash Point Fuels (IGF Code), adopted in 2015. However, LNG presents the shipping industry with the following operational challenges: Onboard storage of cryogenic liquids in the marine environment requires significant modification and replacement of ship bunker fuel storage and fuel transfer systems; LNG supply is not available everywhere in major ports worldwide; and crew qualifications and training for operating LNG or dual-fuel engines must be updated before setting sail.

[0013] Sulfur-free biofuels: Another primary solution proposed to achieve compliance with MARPOL requirements is to replace HMFO with sulfur-free biofuels. Biodiesel has been somewhat successful in replacing petroleum-derived diesel, but its supply remains constrained. Methanol has been used in some coastal operations on coastal vessels such as ferries in the North Sea ECA. The widespread adoption of biofuels such as biodiesel and methanol presents many challenges for shipowners and the bunker fuel industry. These challenges include: the need for fuel system compatibility and adaptation of existing fuel systems; water and biological contamination during long-term storage of methanol and biodiesel; the significantly lower calorific value per ton of methanol and biodiesel compared to HMFO; and the high vapor pressure of methanol, which poses significant safety concerns regarding flash fires.

[0014] Replacing heavy fuel oil with marine light oil or marine diesel: The third proposed primary solution is simply to replace HMFO with marine light oil (MGO) or marine diesel (MDO). The first major problem is the constraint on the global supply of distillates that constitute more than 90% by volume of MGO and MDO. The effective surplus production capacity for producing MGO is less than 100 million metric tons per year, resulting in an annual marine fuel shortage of more than 200 million metric tons per year. Refiners not only lack the capacity to increase MGO production, but also have no economic incentive, as they can obtain higher value and higher profits from ultra-low sulfur diesel fuel for land transport systems (i.e., trucks, trains, public transport, construction heavy machinery, etc.).

[0015] Blending: Another primary solution is to blend HMFO with a low-sulfur fuel, such as low-sulfur marine diesel (0.1 wt% sulfur content), to obtain an HMFO product with a sulfur content of 0.5 wt%. In the linear blending method (based on linear blending), to obtain HMFO with a sulfur concentration of 0.5 wt%, 7.5 tons of MGO or MDO material with a sulfur content of 0.1 wt% are required for every ton of HSFO (3.5% sulfur content). Those skilled in the art of fuel blending will immediately understand that blending impairs the fundamental properties of HMFO, specifically that its viscosity and density change significantly. Furthermore, the blending process may result in changes to the viscosity and density of the fuel, potentially causing it to no longer meet the requirements of HMFO.

[0016] Introducing blended HMFO into fuel supply infrastructure and on-board systems designed for non-blended HMFO with different specifications can also lead to further problems. There is a real risk of incompatibility when mixing two types of fuels. When mainly paraffinic distillate fuels (MGO or MDO) are blended with HMFO with a high aromatic content, it often leads to a deterioration in the solubility of asphaltenes. In the blended fuel, asphaltenes and / or highly paraffinic substances can precipitate from the distillate material, easily forming fuel tank sludge that is difficult to handle. Fuel tank sludge can cause blockages in filters and separators, transfer pumps and lines, accumulate sludge in storage tanks, stick to fuel injection pumps (deposit on plungers and barrels), and clog fuel nozzles. Such risks to the main propulsion system are unacceptable for ocean-going cargo ships.

[0017] Finally, blending HMFO with marine distillate products (MGO or MDO) is not economically viable. The blender would take in a high-value product (marine gas oil (MGO) or marine diesel oil (MDO) with a sulfur content of 0.1%) and blend it with low-value high-sulfur HMFO at a ratio of 7.5:1 to produce an HMFO end product compliant with IMO / MARPOL (i.e., low-sulfur marine heavy fuel oil (LSHMFO) with a sulfur content of 0.5% by weight). It is expected that LSHMFO will be sold at a price per ton lower than the individual values of both blendstocks.

[0018] Residual Oil Treatment: Over the past few decades, the refining industry's research efforts regarding the treatment of heavy oils (crude oil, distress oil or residual oil) have focused on enhancing the properties of these low-value refined process oils to produce lighter and more valuable oils. The challenges were that crude oil, distress oil and residual oil can be unstable and contain high concentrations of sulfur, nitrogen, phosphorus, metals (especially vanadium and nickel) and asphaltenes. Most of the nickel and vanadium are difficult to remove by chelation with porphyrins. Metal-organic compounds such as vanadium and nickel porphyrins are involved in catalyst contamination and corrosion problems in refineries. Sulfur, nitrogen and phosphorus are removed because they are well-known catalyst poisons for noble metal (platinum and palladium) catalysts used in downstream processes of atmospheric or vacuum distillation columns.

[0019] The difficulty of treating atmospheric or vacuum residue streams has been known for many years and has been the subject of numerous research investigations. A number of residual oil conversion processes have been developed with the same goals of 1) producing more valuable, preferably distillate-range hydrocarbon products, and 2) concentrating contaminants such as sulfur, nitrogen, phosphorus, metals, asphaltenes, etc., into forms (coke, heavy coker residue, FCC slurry oil) that are removed from refinery streams. Well-known practices in the refining industry are to increase reaction severity (high temperature and high pressure) to produce lighter and more refined hydrocarbon products, extend catalyst life, and remove sulfur, nitrogen, phosphorus, metals and asphaltenes from refinery streams.

[0020] In the above process, it is well known that the properties of the raw materials have a significant impact on the resulting product, catalyst life, and ultimately the economic viability of the process. Non-patent literature 1, a representative paper, states, "The results revealed that there were significant changes in activity depending on the raw materials used in the test. This study confirmed the importance of appropriately selecting raw materials used for performance evaluation and selection of catalyst candidates for stepwise catalyst systems for residue oil hydrogenation." From this, those skilled in the art will understand that the conditions necessary for the effective hydrogenation of atmospheric residue cannot be applied to the effective hydrogenation of vacuum residue, and the latter conditions cannot be applied to the effective hydrogenation of visbreaker residue. Effective reaction conditions differ depending on the raw materials. For this reason, modern integrated refineries have multiple hydrogenation facilities, each targeting a specific hydrocarbon stream, with an emphasis on producing high-value, desirable light hydrocarbons and providing products acceptable to downstream processes.

[0021] A further problem in the treatment of heavy hydrocarbons such as heavy residue oil is the inherent instability of each intermediate refinery stream. Those skilled in the art will understand that there are many practical reasons for treating each refinery stream separately. One such reason is the unpredictable nature of the asphaltenes contained in each stream. Asphaltenes are large, complex hydrocarbons that tend to precipitate from refinery hydrocarbon streams. As those skilled in the art will know, even small changes in composition or physical conditions (temperature, pressure) can cause asphaltenes, which would otherwise be dissolved in solution, to precipitate. When precipitated from solution, asphaltenes can immediately clog basic lines, control valves, and cover critical detection devices (i.e., temperature and pressure sensors), which can result in significant and costly disruptions and shutdowns of some equipment or even the entire refinery. For this reason, it has been the long-standing practice in refineries to process each intermediate product stream (atmospheric residue, vacuum residue, FCC slurry, etc.) in separate reactors rather than blending them.

[0022] In summary, since the introduction of the MARPOL standard to reduce sulfur concentrations in HMFO worldwide, crude oil refiners have not made any technological efforts to produce low-sulfur substitutes for HMFO. Despite strong economic incentives from governments and the needs of the international shipping industry, refiners have little economic incentive to work on removing environmental pollutants from HMFO. On the contrary, the global refining industry is focused on generating higher value from each barrel of oil by producing light hydrocarbons (i.e., diesel and gasoline), thereby concentrating environmental pollutants into increasingly low-value streams (i.e., residue) and products (petroleum coke, HMFO). Shipping companies are focusing on short-term solutions, such as installing scrubbing equipment and making limited use of more expensive low-sulfur marine diesel and diesel fuel as substitutes for HMFO. In the open ocean, most, if not all, major shipping companies continue to use the most economically viable fuel, namely HMFO. The need for processes and equipment to remove environmental contaminants (i.e., sulfur, nitrogen, phosphorus, metals, especially vanadium and nickel) from HMFO without altering the quality and properties that make HMFO the most economical and practical means of powering ocean-going vessels has remained unmet for many years. Furthermore, the need for IMO-compliant low-sulfur (i.e., 0.5 wt% sulfur) or ultra-low-sulfur (0.10 wt% sulfur) HMFO that also meets the bulk properties required for commercially viable ISO 8217 HMFO has also remained unmet for many years. [Prior art documents] [Non-patent literature]

[0023] [Non-Patent Document 1] Residual-Oil Hydrotreating Kinetics for Graded Catalyst Systems:Effects of Original and Treated Feedstocks [Overview of the project] [Problems that the invention aims to solve]

[0024] To minimize changes in the desirable properties of marine heavy fuel oil (HMFO), and to reduce by-product hydrocarbons (i.e., light hydrocarbons (C1-C8) and crude naphtha (C5-C8) 20 A common objective in processes that minimize the unnecessary generation of HMFOs is to reduce environmental pollutants in HMFOs. [Means for solving the problem]

[0025] The first aspect and exemplary embodiments include a process for reducing environmental pollutants in marine heavy fuel oil raw materials, comprising: mixing a predetermined amount of the marine heavy fuel oil raw material with a predetermined amount of an activated gas mixture to obtain a raw material mixture; contacting the raw material mixture with one or more catalysts to prepare a process mixture from the raw material mixture; receiving the process mixture, separating the marine heavy fuel oil product, which is the liquid component of the process mixture, from the gaseous component and by-product hydrocarbon component of the process mixture; and discharging the marine heavy fuel oil product.

[0026] Second aspects and exemplary embodiments include a hydrocarbon fuel composition (hereinafter referred to as a marine heavy fuel composition) consisting essentially of at least a large amount, preferably 85 vol%, more preferably at least 90 vol%, and most preferably at least 95 vol%, by volume, wherein the marine heavy fuel oil product is obtained from a disclosed process for reducing environmental pollutants in marine heavy fuel oil raw materials, or optionally manufactured by an apparatus for carrying out such process. The remainder of the volume in the marine heavy fuel composition may be a diluent, but when mixed with an HMFO product, the mixture does not conform to the ISO 8217:2017 standard for the bulk properties of marine residual fuel and achieves a sulfur content lower than the MARPOL world standard sulfur content (ISO 14596 or ISO 8754) of 0.5 heavy%.

[0027] A third aspect and exemplary embodiment encompasses an apparatus for reducing environmental pollutants in HMFO raw materials and producing an HMFO product. The exemplary apparatus comprises a first vessel, a second vessel in fluid communication with the first vessel, a third vessel in fluid communication with the second vessel, and a discharge line extending from the third vessel for discharging the HMFO product. The first vessel receives a predetermined amount of the HMFO raw material mixed with a predetermined amount of activated gas mixture, and prepares a process mixture by contacting the resulting mixture with one or more catalysts under specific process conditions. The second vessel receives the process mixture discharged from the first vessel and separates the liquid component from the bulk gas component in the process mixture. The bulk gas component is sent for further processing. The liquid component is sent to the third vessel, which separates residual gas components and by-product hydrocarbon components (mainly light components and crude naphtha) from the processed HMFO product, after which the HMFO product is discharged. [Brief explanation of the drawing]

[0028] [Figure 1] This is a process flow diagram of the process for manufacturing HMFO products. [Figure 2] This is a basic schematic diagram of a plant that manufactures HMFO products. [Modes for carrying out the invention]

[0029] The inventive concepts described herein use terminology that should be familiar to those skilled in the art, but some terms are used with specific meanings in mind, and these terms are defined below.

[0030] Heavy Marine Fuel Oil (HMFO): Regardless of the concentration of environmental pollutants, this is a petroleum product fuel that conforms to the ISO 8217:2017 standard for the bulk characteristics of marine residual fuel.

[0031] Environmental pollutants: These are the organic and inorganic components of HMFO that produce SOx, NOx, and particulate matter when burned.

[0032] HMFO raw material: Regardless of the concentration of environmental pollutants, it is a petroleum product fuel that conforms to the ISO 8217:2017 standard for the bulk characteristics of marine residual fuel. It is preferable that the sulfur content of the HMFO raw material is greater than the MARPOL world standard of 0.5% by weight, and that the sulfur content (ISO 14596 or ISO 8754) is in the range of 5.0% by weight to 1.0% by weight.

[0033] Marine heavy fuel composition: A hydrocarbon fuel composition essentially consisting of at least 85 volume% of HMFO product and 15 volume% or less of diluent, conforming to the ISO 8217:2017 standard for the bulk properties of marine residual fuel, and having a sulfur content less than the MARPOL world standard sulfur content (ISO 14596 or ISO 8754) of 0.5 wt%.

[0034] Diluents: Hydrocarbon or non-hydrocarbon materials mixed, combined, or added to HMFO products, or solids suspended in HMFO products. Their presence does not result in a mixture that does not conform to the ISO 8217:2017 standard for the bulk properties of marine residual fuel, nor does it result in a sulfur content exceeding the MARPOL world standard (ISO 14596 or ISO 8754) of 0.5% heavy sulfur.

[0035] HMFO products: These are petroleum fuel products that conform to the ISO 8217:2017 standard for bulk characteristics of marine residual fuels, achieving a sulfur content lower than the MARPOL world standard sulfur content (ISO 14596 or ISO 8754) of 0.5% by weight, and preferably having a maximum sulfur content (ISO 14596 or ISO 8754) in the range of 0.05% by weight to 1.0% by weight.

[0036] Activated gas: A mixture of gases used in a process combined with a catalyst to remove environmental pollutants from HMFO raw materials.

[0037] Fluid communication: The ability to transfer a fluid (which may be a liquid, gas, or both, including a suspension of solids) from a first container or location to a second container or location, and may include connections made by pipes (also called lines), spools, valves, intermediate holding tanks, or surge tanks (also called drums).

[0038] Suitable product quality: The marine residual fuel oil is of a quality level suitable for its intended normal purpose (i.e., use as a residual fuel source for offshore vessels), and is marketable as a heavy marine or residual bunker fuel, and is substituted for such fuel.

[0039] Bbl or bbl: A standard unit of volume for petroleum. 1 bbl = 0.1589873 m³ 3 Alternatively, 1 bbl = 158.9873 liters or 1 bbl = 42.00 US fluid gallons.

[0040] Bpd: An abbreviation for Bbl per day.

[0041] SCF is an abbreviation for standard cubic foot of gas. One standard cubic foot (14.73 psi and 60°F) is equal to 0.0283058557 standard cubic meters (101.325 kPa and 15°C).

[0042] The concept of the present invention will be described in more detail herein with reference to the drawings. Figure 1 shows a generalized block process flow for reducing environmental contaminants in HMFO raw materials and producing HMFO products according to a first exemplary embodiment. A predetermined amount of HMFO raw material (2) is mixed with a predetermined amount of activated gas (4) to obtain a raw material mixture. The HMFO raw material used typically satisfies the bulk properties and specific basic chemical properties of marine residual fuel oil conforming to ISO 8217:2017, apart from environmental contaminants. More specifically, if the environmental contaminant is sulfur, the sulfur concentration in the HMFO raw material may be in the range of 5.0% by weight to 1.0% by weight. The HMFO raw material has a maximum kinematic viscosity (ISO 3104) of 180 mm at 50°C. 2 / sec~700mm 2 The maximum density at 15°C in the range of / second (ISO3675) is 991.0 kg / m³.3 ~1010.0 kg / m 3 Within the range of, the CCAI should be 780 - 870, and the flash point (ISO2719) should be 60.0 °C or higher, having the bulk physical properties required for ISO8217:2017 compliant HMFO. As other characteristics of the HMFO raw material related to the generation of particulate matter (PM), the maximum total sediment (ISO10307-2) due to aging is 0.10% by weight, the maximum residual carbon content (ISO10370) by the micro method is in the range of 18.00% - 20.00% by weight, and the maximum aluminum + silicon (ISO10478) content is 60 mg / kg. Examples of environmental pollutants other than sulfur that can be contained in the HMFO raw material in light of ISO requirements include vanadium, nickel, iron, aluminum, and silicon, which are significantly reduced by the process of the present invention. However, those skilled in the art will understand that the vanadium content serves as a general indicator for these other environmental pollutants. In a preferred embodiment, the vanadium content is ISO compliant, and the maximum vanadium content (ISO14597) of the MHFO raw material is in the range of 350 mg / kg - 450 ppm mg / kg.

[0043] Regarding the characteristics of the activation gas, the activation gas should be selected from a mixture of nitrogen, hydrogen, carbon dioxide, water vapor, and methane. The mixture of gases in the activation gas should have the ideal gas partial pressure of hydrogen (P H2 ) exceeding 80% of the total pressure (P) of the activation gas mixture, and it is more preferable that the ideal gas partial pressure of hydrogen (P H2 ) in the activation gas exceeds 95% of the total pressure (P) of the activation gas mixture. As will be understood by those skilled in the art, the molar content of the activation gas is another criterion, and the hydrogen molar fraction of the activation gas should be in the range of 80% - 100% of the total number of moles of the activation gas mixture, and it is more preferable that the hydrogen molar fraction of the activation gas is 80% - 99% of the total number of moles of the activation gas mixture.

[0044] The raw material mixture (i.e., a mixture of HMFO raw material and activated gas) is placed in a first vessel, preferably a reaction vessel, under process conditions of temperature and pressure, and then the raw material mixture is brought into contact with one or more catalysts (8) to prepare a process mixture from the raw material mixture.

[0045] The process conditions are selected such that the ratio of the amount of activated gas to the amount of HMFO raw material is 250 scf / bbl to 10,000 scf / bbl of gas relative to the HMFO raw material, preferably 2,000 scf / bbl to 5,000 scf / bbl of gas relative to the HMFO raw material, and more preferably 2,500 scf / bbl to 4,500 scf / bbl of gas relative to the HMFO raw material. The process conditions are selected such that the total pressure in the first vessel is 250 psig to 3,000 psig, preferably 1,000 psig to 2,500 psig, and more preferably 1,500 psig to 2,200 psig. The process conditions are selected such that the indicated temperature in the first vessel is 500°F to 900°F, preferably 650°F to 850°F, and more preferably 680°F to 800°F. To achieve desulfurization with a product sulfur concentration of less than 0.5% by weight, the process conditions are as follows: the liquid space velocity in the first container is 0.05 (oil) / hour / m 3 (catalyst)~1.0(oil) / hour / m 3 (Catalyst), preferably 0.08 (oil) / hour / m 3 (catalyst)~0.5(oil) / hour / m 3 (Catalyst), more preferably 0.1 (oil) / hour / m 3 (catalyst)~0.3(oil) / hour / m 3 It is selected to act as a catalyst.

[0046] Those skilled in the art will understand that process conditions are determined taking into account the hydraulic capacity of the equipment. The hydraulic capacity of the treatment equipment may be, for example, 100 bbl / day to 100,000 bbl / day of HMFO raw material, preferably 1,000 bbl / day to 60,000 bbl / day, more preferably 5,000 bbl / day to 45,000 bbl / day, and even more preferably 10,000 bbl / day to 30,000 bbl / day of HMFO raw material.

[0047] The above process may use one or more catalyst systems selected from the group consisting of boiling-bed supported transition metal heterogeneous catalysts, stationary-bed supported transition metal heterogeneous catalysts, and combinations of boiling-bed supported transition metal heterogeneous catalysts and stationary-bed supported transition metal heterogeneous catalysts. Those skilled in the art will understand that stationary-bed supported transition metal heterogeneous catalysts are the most technically easy and preferable to implement. The transition metal heterogeneous catalyst comprises a porous inorganic oxide catalyst support and a transition metal catalyst. The porous inorganic oxide catalyst support is at least one support selected from the group consisting of alumina, alumina / boria support, support containing metal-containing aluminosilicate, alumina / phosphorus support, alumina / alkaline earth metal compound support, alumina / titania support, and alumina / zirconia support. The transition metal component of the catalyst is one or more metals selected from the group consisting of groups 6, 8, 9, and 10 of the periodic table. In a preferred exemplary embodiment, the transition metal heterogeneous catalyst comprises a porous inorganic oxide catalyst support and a transition metal catalyst, wherein the porous inorganic oxide catalyst support is preferably alumina, and the transition metal catalyst is preferably Ni--Mo, Co--Mo, Ni--W, or Ni-Co-Mo.

[0048] The process mixture (10) is removed from the first vessel (8), freed from contact with one or more catalysts, and sent by fluid communication to a second vessel (12), preferably a gas-liquid separator or a high-temperature separator and a low-temperature separator, for separating the liquid component (14) of the process mixture from the bulk gas component (16) of the process mixture. The gas component (16) is processed beyond the battery limit of the current process. This gas component may consist of a mixture of lighter hydrocarbons (mostly methane, ethane, and propane, but partly crude naphtha) and an activated gas component, which may be inevitably produced as part of the by-product hydrocarbons by the above process.

[0049] The liquid component (16) is delivered by fluid communication to a third vessel (18), preferably a fuel oil product stripper system, for separating residual gaseous components (20) and by-product hydrocarbon components (22) from the HMFO product (24). The residual gaseous components (20) may be a mixture of gases selected from the group consisting of nitrogen, hydrogen, carbon dioxide, hydrogen sulfide, water vapor, and C1-C5 light hydrocarbons. This residual gas is processed outside the battery limit of the current process and mixed with other gaseous components (16) removed from the process mixture (10) in the second vessel (12). The liquid by-product hydrocarbon components (22) are condensable hydrocarbons inevitably produced in the above process, which can be used as part of the automotive fuel blend pool or sold on the open market as gasoline and diesel blend components (C5-C5). 20 The mixture may be selected from the group consisting of hydrocarbons (crude naphtha), (naphtha-diesel) and other condensable light liquid (C4-C8) hydrocarbons.

[0050] The residual gaseous components are a mixture of gases selected from the group consisting of nitrogen, hydrogen, carbon dioxide, hydrogen sulfide, water vapor, and light hydrocarbons. The amine scrubber effectively removes the hydrogen sulfide, which can then be treated using techniques and processes well known to those skilled in the art. In one preferred exemplary embodiment, the hydrogen sulfide is converted to elemental sulfur using the well-known Krauss process. In another embodiment, a patented process is used to convert hydrogen sulfide to hydrosulfide acid. In either case, sulfur is removed without entering the environment before the HMFO is burned in the ship's engine. The purified gas is discharged, burned, or more preferably recycled and used as an activated gas.

[0051] The by-product hydrocarbon components can be sent to the automotive fuel blend pool, sold across the fence to an adjacent refinery, or used to ignite heaters and combustion turbines, thereby supplying heat and power to the above processes. 20It is a mixture of hydrocarbons (crude naphtha) (naphtha-diesel). These by-product hydrocarbons are produced by hydrocracking reactions, but should be less than 10% by weight, preferably less than 5% by weight, and more preferably less than 2% by weight of the total process material balance.

[0052] The HMFO product (24) is discharged into the storage tank via fluid communication when it exceeds the battery limit of the current process.

[0053] HMFO product: The HMFO product obtained from the disclosed exemplary process has a suitable quality for sale and use as marine heavy fuel oil (also known as marine residual fuel oil or heavy bunker fuel), and the HMFO product has a maximum kinematic viscosity (ISO3104) of 180 mmHg at 50C. 2 / sec~700mm 2 The maximum density at 15°C in the range of / second (ISO3675) is 991.0 kg / m³. 3 ~1010.0 kg / m 3 It exhibits the bulk properties necessary to become ISO-compliant (i.e., ISO 8217:2017) marine residual fuel oil, with bulk characteristics including a CCAI in the range of 780-870, a flash point (ISO 2719) of 60.0°C or higher, a maximum total sediment content (ISO 10307-2) of 0.10 wt% by aging, a maximum residual carbon content (ISO 10370) in the range of 18.00 wt%-20.00 wt%, and a maximum aluminum + silicon (ISO 10478) content of 60 mg / kg.

[0054] The HMFO product has a sulfur content (ISO 14596 or ISO 8754) of less than 0.5% by weight, preferably less than 0.1% by weight, and more preferably less than 0.05% by weight, and fully conforms to the requirements of IMO Annex VI (revised) as a low-sulfur, preferably very low-sulfur HMFO. That is, the sulfur content of the HMFO product is reduced by about 90% or more compared to the HMFO raw material. Similarly, the vanadium content (ISO 14597) of the marine heavy fuel oil product is less than 10% of the maximum vanadium content of the marine heavy fuel oil raw material, more preferably less than 1%. Those skilled in the art will understand that the significant reduction in sulfur and vanadium content of the HMFO raw material indicates that the process has achieved a significant reduction in environmental pollutants in the HMFO raw material, and equally importantly, that this has been achieved while maintaining the desirable properties of ISO 8217:2017 compliant HMFO.

[0055] HMFO products not only conform to ISO 8217:2017 (and are suitable for use as marine residual fuel oil or bunker fuel), but also have a maximum sulfur content (ISO 14596 or ISO 8754) in the range of 0.05% to 1.0% by weight, preferably in the range of 0.05% ppm to 0.5% by weight, and more preferably in the range of 0.1% to 0.05% by weight. The vanadium content of HMFO products is well within the range of the maximum vanadium content (ISO 14597) required for ISO 8217:2017 marine residual fuel oil, which has a vanadium content of less than 450 ppm mg / kg. Preferably, the vanadium content (ISO 14597) is less than 300 mg / kg, and more preferably in the range of 50 mg / kg to 100 mg / kg.

[0056] Those skilled in the art with respect to marine fuel blends, bunker fuel formulations, and fuel logistics requirements for shipping fuels will readily understand that HMFO products can be marketed and used as low-sulfur MARPOL Annex VI compliant marine heavy (residue) fuel oils that can be directly used as a substitute for currently used high-sulfur marine heavy (residue) fuel oils or heavy bunker fuels, without further alteration of composition or blending. One exemplary embodiment is an ISO 8217:2017 compliant low-sulfur marine heavy fuel oil containing (preferably essentially therefrom) 100% hydrogenated ISO 8217:2017 compliant high-sulfur marine heavy fuel oil, wherein the sulfur concentration of the hydrogenated ISO 8217:2017 compliant high-sulfur marine heavy fuel oil exceeds 0.5% by weight, and the sulfur concentration of the ISO 8217:2017 compliant low-sulfur marine heavy fuel oil is less than 0.5% by weight. Another exemplary embodiment is an ISO 8217:2017 compliant ultra-low sulfur marine heavy fuel oil comprising (preferably essentially comprising) a 100% hydrogenated ISO 8217:2017 compliant high sulfur marine heavy fuel oil, wherein the sulfur concentration of the hydrogenated ISO 8217:2017 compliant high sulfur marine heavy fuel oil exceeds 0.5% by weight, and the sulfur concentration of the ISO 8217:2017 compliant low sulfur marine heavy fuel oil is less than 0.1% by weight.

[0057] As a result of the present invention, several economic and logistical benefits will be realized for the fuel supply and shipping industries. More specifically, the achievable benefits include minimal changes to existing marine heavy fuel supply infrastructure (storage and transfer systems) and onboard systems required to comply with the emission requirements of MARPOL Annex VI (revised), and no additional training or qualifications required for crew members. Furthermore, several economic and logistical benefits that refiners could potentially realize include, to name a few, the elimination of the need to change or adjust refinery operations and product streams to meet new market demand for low-sulfur or ultra-low-sulfur HMFOs; the fact that the exemplary processes described above can be carried out as standalone facilities, eliminating the need to add equipment to refineries as hydrogen or sulfur capacity is added; the ability to maintain the focus of refinery operations on products that generate the greatest value from the received crude oil (i.e., the production of petrochemicals, gasoline, and distillates (diesel)); and the ability for refiners to continue using crude oil from their existing candidate list without having to switch to sweeter or lighter crude oil to meet the environmental requirements for HMFO products.

[0058] Marine Heavy Fuel Compositions: One aspect of the concept of the present invention is a fuel composition comprising, preferably essentially therefrom, an HMFO product obtained from the disclosed process, and possibly comprising a diluent. As described above, the bulk properties of the HMFO product itself conform to ISO 8217:2017 and satisfy the worldwide IMO Annex VI requirements for maximum sulfur content (ISO 14596 or ISO 8754). If very low concentrations of sulfur are required, the process of the present invention achieves this, but those skilled in the art of marine fuel blends will understand that low-sulfur marine heavy fuel compositions conforming to the worldwide IMO Annex VI can be prepared by using a low-sulfur or very low-sulfur HMFO product as the main blend stock. Such a low-sulfur marine heavy fuel composition would comprise (preferably essentially therefrom) a) an HMFO product and b) a diluent. In one embodiment, the majority of the volume of the marine heavy fuel composition is the HMFO product, with the remainder being the diluent. The marine heavy fuel composition preferably consists of at least 75% by volume, preferably at least 80% by volume, more preferably at least 90% by volume, and even more preferably at least 95% by volume, of an HMFO product, with the remainder being a diluent.

[0059] The diluent may be a hydrocarbon or non-hydrocarbon material mixed with, combined with, or added to the HMFO product, or a solid particulate material suspended in the HMFO product. The diluent may intentionally or unintentionally alter the composition of the HMFO product, but the resulting mixture will not fail to conform to the ISO 8217:2017 standard for the bulk properties of marine residual fuel, nor will it have a sulfur content less than 0.5% heavy sulfur according to the MARPOL world standard (ISO 14596 or ISO 8754). Examples of diluents considered as hydrocarbon-based materials include: HMFO raw materials (i.e., high-sulfur HMFO); distillate-based fuels such as traffic diesel, light oil, MGO, or MDO; cutter oil (currently used in the blending of marine residual fuel oil); renewable oils and fuels such as biodiesel, methanol, and ethanol; synthetic hydrocarbons and oils based on gas liquefaction technology, such as fully synthetic oils based on Fischer-Tropsch oil, polyethylene, polypropylene, dimers, trimers, polybutylene, etc.; hydrocarbon oils such as refinery residues, such as atmospheric residues, vacuum residues, and fluid catalytic cracking (FCC) oils. Examples include slurry oil, FCC cycle oil, pyrolytic diesel fuel, cracked light diesel fuel (CLGO), cracked heavy diesel fuel (CHGO), light cycle oil (LCO), heavy cycle oil (HCO), pyrolytic residue, heavy coker distillate, bitumen, heavy deasphalt oil, visbreaker residue, slop oil, asphalt oil; used or recycled motor oil; lubricating oil aromatic extracts, crude oils such as heavy crude oil and distressed crude oil, and similar materials that, in the case of prior art high-sulfur marine heavy (residue) fuel oil, would be sent to a hydrocracking unit or converted to a blend pool.Examples of diluents considered as non-hydrocarbon materials include residual water (i.e., water absorbed from moisture in the air, or water mixed or solubilized in the hydrocarbons of the HMFO product, possibly as a microemulsion), fuel additives, for example, but not limited to, detergents, viscosity modifiers, pour point depressants, lubricity modifiers, haze removers (alkoxylated phenolformamide polymers, etc.), defoamers (polyether-modified polysiloxanes, etc.); ignition enhancers; rust inhibitors (succinate ester derivatives, etc.); corrosion inhibitors; wear-resistant additives, antioxidants (phenol compounds and derivatives, etc.), coatings and surface modifiers, metal deactivators, antistatic agents, ionic and nonionic surfactants, stabilizers, cosmetic colorants and deodorizers, and mixtures thereof. The third group of diluents includes suspended solids or particulate matter contained as a result of handling, storage, and transportation of HMFO products or marine heavy fuel compositions, such as, but not limited to, carbon or hydrocarbon solids (coke, graphite solids, finely aggregated asphaltene, etc.) that do not impair the suitability of marine heavy fuel compositions as ISO 8217:2017 compliant marine heavy (residue) fuels, oxidized corrosion solids such as iron rust, bulk metal fine particles, paint or surface coating particles, plastic or polymer or elastomer or rubber particles (such as those produced by the decomposition of gaskets, valve parts, etc.), catalyst fine particles, ceramic or mineral particles, soil particles such as sand and clay, biologically produced solids such as microorganisms, and mixtures thereof.

[0060] The blend of HMFO products and diluents must be of suitable quality as a low-sulfur marine heavy (residue) fuel. That is, the blend must be suitable for its intended use as marine heavy bunker fuel and, in general, should be replaceable as bunker fuel for ocean-going vessels. Preferably, the marine heavy fuel composition must have the bulk properties required for marine residual fuel oil compliant with ISO 8217:2017 and a sulfur content less than 0.5% heavy sulfur according to the MARPOL world standard (ISO 14596 or ISO 8754) so ​​that it can be certified as low-sulfur marine heavy fuel oil (LS-HMFO) under MARPOL Annex VI. As described above, the sulfur content of the HMFO product may be significantly less than 0.5% by weight (i.e., less than 0.1% heavy sulfur (ISO14596 or ISO8754)) to be certified as ultra-low sulfur marine heavy fuel oil (ULS-HMFO) under MARPOL Annex VI (revised edition), and similarly, the marine heavy fuel composition may be formulated to be certified as MARPOL Annex VI compliant ULS-HMFO suitable for use as marine bunker fuel in ECA areas. To be certified as an ISO8217:2017 certified fuel, the marine heavy fuel composition of the present invention has a maximum kinematic viscosity (ISO3104) of 180 mmHg at 50C. 2 / sec~700mm 2 The maximum density at 15°C in the range of / second (ISO3675) is 991.0 kg / m³. 3 ~1010.0 kg / m 3 It must meet internationally recognized standards, including a range of 780-870 for CCAI, a flash point (ISO2719) of 60.0°C or higher, a maximum total sediment content (ISO10307-2) of 0.10 wt%, a maximum residual carbon content (ISO10370) of 18.00 wt%-20.00 wt%, and a maximum aluminum + silicon content (ISO10478) of 60 mg / kg.

[0061] Description of the production plant: Referring next to a more detailed exemplary embodiment of the production plant, Figure 2 shows a schematic diagram of a production plant that carries out the above process for reducing environmental pollutants in HMFO raw materials and producing HMFO products according to a second exemplary embodiment. Another embodiment of the production plant using multiple reactors is within the scope of the present invention and will be described in concurrent disclosures.

[0062] In Figure 2, the HMFO raw material (A) is supplied from outside the battery limit (OSBL) to the oil feed surge drum (1), which receives the feed from outside the battery limit (OSBL) and provides sufficient surge capacity to ensure smooth operation of the equipment. Water entrained in the feed is removed from the HMFO and discharged as a stream (1c) that is treated at the OSBL.

[0063] The HMFO raw material (A) is taken from the oil feed surge drum (1) via line (1b) by an oil feed pump (3) and pressurized to the pressure required for the above process. The pressurized HMFO (A') then passes through line (3a) to the oil feed / product heat exchanger (5), where the pressurized HMFO feed (A') is partially heated by the HMFO product (B). The HMFO product (B) is a hydrocarbon stream with a sulfur content of less than 5000 ppmw, preferably less than 1000 ppmw. Hydrocarbons in the HMFO raw material and HMFO product are C 12 ~C 70+ The boiling point range is 350°F to 1110+F. The pressurized HMFO feedstock (A') passing through line (5a) is further heated in the reactor feed / effluent heat exchanger (7) by the efferent coming out of the reactor system (E).

[0064] The heated and pressurized HMFO raw material (A'') in line (7a) is then mixed with activated gas (C) supplied through line (23c) at the mixing point (X) to prepare a raw material mixture (D). The mixing point (X) may be any gas / liquid mixing system or entrainment mechanism known to those skilled in the art.

[0065] The raw material mixture (D) passes through line (9a) to the reactor feed furnace (9), where it is heated to a specific process temperature. The reactor feed furnace (9) may be any type of heater known to those skilled in the art, such as a combustion heater, as long as it raises the temperature of the raw material mixture to the temperature required for the process conditions.

[0066] The fully heated raw material mixture (D') exits the reactor feed furnace (9) via line 9b and is supplied to the reactor system (11). The fully heated raw material mixture (D') enters the reactor system (11), where environmental contaminants such as sulfur, nitrogen, and metals are preferentially removed from the HMFO raw material components of the fully heated raw material mixture. The reactor system includes a catalyst, which preferentially removes sulfur compounds in the HMFO raw material components by reacting them with hydrogen in an activated gas to produce hydrogen sulfide. Demetallation, denitrification, and some ring-opening hydrogenation of complex aromatic compounds and asphaltenes also occur in the reactor system, but hydrocracking of hydrocarbons should be minimized. Process conditions such as hydrogen partial pressure, reaction pressure, temperature, and residence time (measured by spatiotemporal velocity) are optimized to obtain the desired final product quality. A more detailed discussion of the process aspects, including the reactor system, catalyst, and process conditions, is included in the following "Description of the Reactor System".

[0067] The reactor system efluent (E) exits the reactor system (11) via line (11a) and is partially heated in the reactor feed / efluent exchanger (7) by exchanging heat with the pressurized HMFO feedstock (A'). The partially cooled reactor system efluent (E') then flows through line (11c) to the high-temperature separator (13).

[0068] The high-temperature separator (13) separates the gaseous component (F) of the reactor system efluent sent to line (13a) from the liquid component (G) of the reactor system efluent sent to line (13b). The gaseous component of the reactor system efluent in line (13a) is cooled by air in the high-temperature separator vapor air cooler (15) and then flows through line (15a) to the low-temperature separator (17).

[0069] The cryogenic separator (17) further separates the residual gaseous component from the liquid component in the cooled gaseous component (F') of the reactor system efluent. The gaseous component (F'') exiting the cryogenic separator is sent to line (17a) and supplied to the amine absorber (21). The cryogenic separator (17) also separates the residual cryogenic separator hydrocarbon liquid (H) from the liquid water (I) condensed in the cryogenic separator into line (17b). The liquid water (I) condensed in the cryogenic separator is sent to the OSBL via line (17c) for processing.

[0070] The hydrocarbon liquid component (G) of the reactor system efluent from the high-temperature separator in line (13b) and the low-temperature separator hydrocarbon liquid (H) in line (17b) are mixed and supplied to the oil product stripper system (19). The oil product stripper system (19) removes residual hydrogen and hydrogen sulfide from the HMFO product (B), which is then discharged in line (19b) and stored in the OSBL. The vent stream (M) from the oil product stripper in line (19a) may be sent to the fuel gas system or flare system in the OSBL. A more detailed discussion of the oil product stripper system is included in "Description of the Oil Product Stripper System".

[0071] The gaseous component (F'') exiting the low-temperature separator in line (17a) contains a mixture of hydrogen, hydrogen sulfide, and light hydrocarbons (mostly methane and ethane). This vapor stream (17a) is supplied to the amine absorber (21), where it comes into contact with dilute amine (J) supplied to the amine absorber (21) from the OSBL via line (21a) to remove hydrogen sulfide from the gas constituting the activated gas recirculation stream (C'). The concentrated amine (K) that has absorbed hydrogen sulfide exits the bottom of the amine absorber (21) and is sent to the OSBL via line (21b) for amine regeneration and sulfur recovery.

[0072] Preferably, the amine absorber top vapor in line (21c) is recirculated to the process as recirculated activated gas (C') via the recirculation compressor (23) and line (23a), and is mixed in line (23a) with supplemental activated gas (C'') supplied from OSBL via line (23b). This mixture of recirculated activated gas (C') and supplemental activated gas (C'') prepares the activated gas (C) used in the process via line (23c) as described above. The purified purge gas stream (H) is taken out from the amine absorber top vapor line (21c) and sent to OSBL via line (21d) to prevent the accumulation of non-condensable substances such as light hydrocarbons.

[0073] Description of the reactor system: The reactor system (11) shown in Figure 2 will be readily understood by those skilled in the art, and comprises a single reaction vessel filled with a process catalyst, and sufficient control devices, valves, and sensors.

[0074] Another reactor system in which multiple reaction vessels are used in parallel as shown in Figure 3A, or in a cascaded series configuration as shown in Figure 3B, can be readily replaced with the single-reactor-type reactor system (11) shown in Figure 2. In such embodiments, each of the multiple reaction vessels is placed in parallel and similarly filled with process catalyst, and a heated raw material mixture (D') is supplied through a common line. The efluents from each of the three reactors are remixed in the common line to prepare a mixed reactor efluent (E), which is further processed as described above. In the illustrated configuration, the hydraulic capacity of the entire reactor system can be effectively increased by having the three reactors carry out the above process in parallel. By using control valves and shut-off valves, it is also possible to prevent feed from entering one reaction vessel but allow it to enter the other. In this way, one reactor can be bypassed and shut down for catalyst maintenance and refilling, while the remaining reactor continues to receive the heated raw material mixture (D'). Those skilled in the art will understand that the configuration of this parallel reaction vessel is not limited to three, and that multiple additional reaction vessels can be added. The only limitations on the number of parallel reaction vessels are the spacing between compartments and the capacity to supply the heated raw material mixture (D') to each active reactor.

[0075] In another exemplary embodiment, the cascaded reaction vessels are filled with process catalysts having the same or different activity against environmental contaminants such as metals and sulfur to be removed. For example, one reactor may be filled with a highly active demetallation catalyst, a second subsequent or downstream reactor may be filled with an equilibrium demetallation / desulfurization catalyst, and a third reactor downstream of the second reactor may be filled with a highly active desulfurization catalyst. This allows for better control and equilibrium of process conditions (temperature, pressure, spatial flow rate, etc.) to suit each catalyst. In this way, the parameters of each reactor can be optimized according to the material supplied to a particular reactor / catalyst combination, and hydrocracking can be minimized. Similar to the above exemplary embodiment, multiple reactors arranged in series in a cascade can be used in parallel, thus obtaining the benefits of the above-described configuration (i.e., one row can be kept "operating" while the other row is "shut down" for maintenance, or plant capacity can be increased).

[0076] The reactors constituting the reactor system may be fixed-bed reactors, boiling-bed reactors, or slurry-bed reactors, or combinations of these types of reactors. As can be expected, fixed-bed reactors are preferred because they are easy to operate and maintain.

[0077] The reaction vessel in the reactor system is filled with one or more process catalysts. The precise design of the process catalyst system is a function of raw material properties, product requirements, and operating constraints, and the optimization of the process catalyst can be performed by ordinary trial and error by those skilled in the art.

[0078] The process catalyst comprises at least one metal selected from the group consisting of metals belonging to groups 6, 8, 9, and 10 of the periodic table, and more preferably, a mixed transition metal catalyst such as Ni--Mo, Co--Mo, Ni--W, or Ni-Co-Mo is used. The metal is preferably supported on a porous inorganic oxide catalyst support. The porous inorganic oxide catalyst support is at least one support selected from the group consisting of alumina, alumina / boria support, support containing metal-containing aluminosilicate, alumina / phosphorus support, alumina / alkaline earth metal compound support, alumina / titania support, and alumina / zirconia support. Alumina is a preferred porous inorganic oxide catalyst support. The properties of the HMFO product can be optimized by systematically changing the pore size of the support and the amount of metal packed using desired raw materials and process conditions and testing. Such operations are well known and common to those skilled in the art. The catalyst in the fixed-bed reactor may be close-packed or sock-packed.

[0079] The selection of catalysts used for packing within the reactor system may prioritize desulfurization by designing a catalyst packing scheme in which the raw material mixture first comes into contact with a catalyst bed having a catalyst that prioritizes demetallation, then downstream with a catalyst bed having mixed demetallation and desulfurization activity, and finally downstream with a catalyst bed having high desulfurization activity. In practice, the first bed with high demetallation activity functions as a protective bed for the desulfurization bed.

[0080] The purpose of the reactor system is to process HMFO raw materials with the severity required to meet HMFO product specifications. Demetallation, denitrification, and hydrocarbon hydrogenation reactions may also occur to some extent when the reactor system performance is optimized to achieve the required level of desulfurization. Hydrocracking is preferably minimized in order to reduce the amount of hydrocarbons produced as by-product hydrocarbons in the above process. The purpose of the above process is to selectively remove environmental pollutants from HMFO raw materials and minimize the generation of unnecessary by-product hydrocarbons (C1-C8 hydrocarbons).

[0081] The process conditions in each reaction vessel will depend on the raw materials, the catalyst used, and the desired final characteristics of the desired HMFO product. Changes in conditions are expected by those skilled in the art and can be determined through pilot plant testing and systematic optimization of the process. In this regard, the operating pressure, indicated operating temperature, the ratio of activated gas to HMFO raw materials, the partial pressure of hydrogen in the activated gas, and the space velocity are all important parameters to consider. The operating pressure of the reactor system should be in the range of 250 psig to 3000 psig, preferably 1000 psig to 2500 psig, and more preferably 1500 psig to 2200 psig. The indicated operating temperature of the reactor system should be in the range of 500°F to 900°F, preferably 650°F to 850°F, and more preferably 680°F to 800°F. The ratio of the amount of activated gas to the amount of HMFO raw material should be in the range of 250 scf / bbl to 10,000 scf / bbl of gas relative to the HMFO raw material, preferably 2,000 scf / bbl to 5,000 scf / bbl of gas relative to the HMFO raw material, and more preferably 2,500 scf / bbl to 4,500 scf / bbl of gas relative to the HMFO raw material. The activated gas has an ideal gas partial pressure (P) of hydrogen in the activated gas. H2 The ideal gas partial pressure (P) of the activated gas mixture should be selected from a mixture of nitrogen, hydrogen, carbon dioxide, water vapor, and methane such that the ideal gas partial pressure (P) of the activated gas is greater than 80% of the total pressure (P) of the activated gas mixture. H2 It is preferable that the pressure (P) exceeds 95% of the total pressure (P) of the activated gas mixture. The hydrogen mole fraction of the activated gas may be in the range of 80% of the total number of moles of the activated gas mixture, and it is more preferable that the hydrogen mole fraction of the activated gas is 80% to 99% of the total number of moles of the activated gas mixture. The liquid space velocity in the reactor system should be 0.05 (oil) / hour / m to achieve desulfurization with a product sulfur concentration of less than 0.1% by weight. 3 (catalyst)~1.0(oil) / hour / m 3 (Catalyst), preferably 0.08 (oil) / hour / m 3 (catalyst)~0.5(oil) / hour / m 3 (Catalyst), more preferably 0.1 (oil) / hour / m 3 (catalyst)~0.3(oil) / hour / m 3It should be a catalyst.

[0082] The hydraulic capacity rate of the reactor system should be 100 bbl / day to 100,000 bbl / day of HMFO feedstock, preferably 1,000 bbl / day to 60,000 bbl / day, more preferably 5,000 bbl / day to 45,000 bbl / day, and even more preferably 10,000 bbl / day to 30,000 bbl / day. The desired hydraulic capacity can be achieved in a single-vessel reactor system or a multi-vessel reactor system.

[0083] Description of Oil Product Stripper System: The oil product stripper system (19) comprises a stripper column, accessories, and utilities necessary for removing hydrogen, hydrogen sulfide, and light hydrocarbons lighter than diesel from HMFO products. Such systems are well known to those skilled in the art, and a general description of their functions is provided herein. Liquids from the high-temperature separator (13) and low-temperature separator (7) are supplied to the oil product stripper column (19). Stripping of hydrogen, hydrogen sulfide, and light hydrocarbons lighter than diesel can be achieved using a stripping medium such as a reboiler or raw steam. The oil product stripper system (19) may be designed with a top-of-column system having a top-of-column condenser, reflux drum, and reflux pump, or it may be designed without a top-of-column system. The conditions of the oil product stripper can be optimized to control the bulk properties of the HMFO product, more specifically viscosity and density.

[0084] Description of Amine Absorber System: The amine absorber system (21) has a gas-liquid contact tower, auxiliary equipment, and utilities necessary for removing acidic gases (i.e., hydrogen sulfide) from the cryogenic separator vapor feed so that the resulting purified gas can be recirculated and used as an activated gas. Such systems are well known to those skilled in the art, and a general description of their functions is provided herein. Vapor from the cryogenic separator (17) is supplied to the contact tower / system (19). The cryogenic separator vapor is purified to effectively remove hydrogen sulfide using a dilute amine (or other suitable acidic gas stripping fluid or system) supplied from the OSBL. The amine absorber system (19) may be designed with a gas drying system to remove water vapor entrained in the recirculated activated gas (C').

[0085] More specific exemplary embodiments for carrying out the processes disclosed herein are shown below by the following examples to those skilled in the art. [Examples]

[0086] (Example 1) Overview: The purpose of the pilot test is to demonstrate that it is possible to produce MARPOL-compliant HMFO products by processing HMFO raw materials in a reactor filled with a commercially available catalyst under specific conditions to remove environmental pollutants, particularly sulfur, from HMFO, thereby demonstrating the production of low-sulfur marine heavy fuel oil (LS-HMFO) or ultra-low-sulfur marine heavy fuel oil (USL-HMFO).

[0087] Pilot equipment setup: Two 434cm³ pipes arranged in series to process HMFO raw materials. 3A pilot setup is constructed using reactors. The first reactor is packed with a blend of commercially available hydrometallurgical (HDM) catalyst and commercially available hydrotransition (HDT) catalyst. Those skilled in the art will understand that the HDT catalyst layer can be formed and optimized by combining the HDM and HDS catalyst mixture with an inert material to achieve the desired intermediate / transition activity level. The second reactor is packed with a blend of commercially available hydrotransition (HDT) and commercially available hydrodesulfurization (HDS). Alternatively, only commercially available hydrodesulfurization (HDS) catalyst can be packed into the second reactor. Those skilled in the art will understand that the specific feed characteristics of the HMFO feedstock affect the ratio of HDM, HDT, and HDS catalysts in the reactor system. A systematic process of testing different combinations with the same feedstock will yield an optimized catalyst combination for any feedstock and reaction conditions. In this example, the first reactor is packed with 2 / 3 hydrometallurgical catalyst and 1 / 3 hydrotransition catalyst. The second reactor is packed entirely with hydrodesulfurization catalyst. The catalyst in each reactor is mixed with glass beads (approximately 50 vol%) to improve liquid distribution and better control of the reactor temperature. For this pilot test run, the following commercially available catalysts should be used: HDM: Albemarle KFR20 series or equivalent, HDT: Albemarle KFR30 series or equivalent, HDS: Albemarle KFR50 or KFR70 or equivalent. Once the pilot equipment setup is complete, the catalyst can be activated by sulfidating it with dimethyl disulfide (DMDS) in a manner well known to those skilled in the art.

[0088] Pilot plant operation: Once the activation process is complete, the pilot plant will be ready to receive HMFO raw materials and activated gas feed. In this example, the activated gas may be industrial-grade or higher hydrogen gas. The mixed HMFO raw materials and activated gas are supplied to the pilot plant at the rates and operating conditions described below: Oil supply rate: 108.5 ml / h (space velocity = 0.25 / h), hydrogen / oil ratio: 570 Nm3 / m3 (3200 scf / bbl), reactor temperature: 372°C (702°F), reactor outlet pressure: 13.8 MPa (g) (2000 psig).

[0089] Those skilled in the art will understand that the desired product requirements can be achieved by systematically adjusting and optimizing the speed and conditions according to the feed characteristics. The above equipment is kept in a steady state for each condition, and all samples are taken to complete the analytical test. The mass balance for each condition should be closed before moving to the next condition.

[0090] The expected effects on the HMFO raw material properties are as follows: Sulfur content (weight %): reduced by at least 80%, Metal content (weight %): reduced by at least 80%, MCR / asphaltene content (weight %): reduced by at least 30%, Nitrogen content (weight %): reduced by at least 20%, C1-naphtha yield (weight %): 3.0% or less, preferably 1.0% or less.

[0091] By systematically adjusting the process conditions in the pilot facility as shown in Table 4, the effects of the process conditions can be evaluated, and the performance of the process can be optimized for the specific catalyst and HMFO raw material used.

[0092] [Table A]

[0093] In this way, by optimizing the conditions of the pilot facility, an HMFO product with a sulfur content of less than 0.5% by weight, preferably an HMFO product with a sulfur content of 0.1% by weight, can be obtained. The conditions for producing ULS-HMFO (i.e., an HMFO product with a sulfur content of 0.1% by weight) are as follows: HMFO raw material supply rate: 65.1 ml / h (space velocity = 0.15 / h), hydrogen / oil ratio: 620 Nm 3 / m 3 (3480 scf / bbl), reactor temperature: 385°C (725°F), reactor outlet pressure: 15 MPa (g) (2200 psig).

[0094] Table 5 summarizes the expected effects on the basic characteristics of the HMFO.

[0095] [Table B]

[0096] Table 6 lists the analytical tests performed to characterize HMFO raw materials and HMFO products. These analytical tests include those required by ISO for HMFO raw materials and HMFO products to be certified as ISO-compliant marine residual fuels and to be commercially traded. Additional parameters are provided to enable those skilled in the art to understand and recognize the effectiveness of the process of the present invention.

[0097] [Table C]

[0098] Table 7 shows the production of LS HMFO, including the analytical test results of the HMFO raw materials and the HMFO product expected from the process of the present invention. Those skilled in the art will see that under the above conditions, the level of hydrocarbon decomposition can be minimized to less than approximately 10%, more preferably less than 5%, and even more preferably less than 1% of the total mass balance.

[0099] [Table D-1]

[0100] [Table D-2]

[0101] The HMFO product produced by the process of the present invention can reach the ULS HMFO limit (i.e., an HMFO product with 0.1% by weight of sulfur) by systematically changing process parameters, for example, by reducing the space velocity or the initial sulfur content of the HMFO raw materials used.

[0102] (Example 2: RMG-380 HMFO) Pilot equipment setup: The pilot equipment was set up in the same manner as in Example 1 described above, with the following changes: The first reactor was packed with 70 vol% Albemarle KFR20 series hydrogenation demetallation catalyst as the first (upper) layer in contact with the raw materials, and 30 vol% Albemarle KFR30 series hydrogenation transition catalyst as the second (lower) layer. The second reactor was packed with 20% Albemarle KFR30 series hydrogenation transition catalyst as the first (upper) layer, and 80 vol% hydrogenation desulfurization catalyst as the second (lower) layer. The catalysts were activated by sulfidizing them with dimethyl disulfide (DMDS) in a manner well known to those skilled in the art.

[0103] Pilot plant operation: Upon completion of the activation process, the pilot plant was ready to receive HMFO raw materials and activation gas feed. The activation gas was industrial-grade or higher hydrogen gas. The HMFO raw material was commercially available, commercially viable, ISO 8217:2017 compliant HMFO with a high sulfur content (2.9 wt%). The mixed HMFO raw materials and activation gas were supplied to the pilot plant at the rates and conditions described in Table 8 below. The sulfur concentration in the HMFO product material was optimized by varying the conditions.

[0104] [Table E]

[0105] The analytical data for representative samples of HMFO raw materials and HMFO products are shown below.

[0106] [Table F-1]

[0107] [Table F-2]

[0108] As shown in Table 7 above, the bulk characteristics observed for both the HMFO raw material and the HMFO product were in compliance with ISO 8217:2017 as commercially viable marine residual fuel oil, except that the sulfur content of the HMFO product was significantly reduced compared to the HMFO raw material, as described above.

[0109] Those skilled in the art will understand that the HMFO product manufactured by the process of the present invention achieves not only ISO 8217:2017 compliant LS HMFO (i.e., 0.5 wt% sulfur content) but also ISO 8217:2017 compliant ULS HMFO limit (i.e., 0.1 wt% sulfur content).

[0110] (Example 3: RMG-500 HMFO) The raw material used in the pilot reactor in Example 2 above was changed to commercially available ISO8217:2017 RMK-500 compliant HMFO, which is suitable for commercial use despite containing a high amount of environmental pollutants (i.e., sulfur (3.3 wt%)). Other bulk properties of the RMK-500 high-sulfur HMFO raw material are shown below.

[0111] [Table G]

[0112] The mixed (RMK-500) HMFO raw materials and activated gas were supplied to the pilot plant at the rates and conditions shown in the table below, and the sulfur concentrations shown in the table below were obtained.

[0113] [Table H]

[0114] The bulk properties observed in the obtained (RMK-500)HMFO product were consistent with the (RMK-500)HMFO raw material, except that the sulfur content was significantly reduced as shown in the table above.

[0115] Those skilled in the art will understand that the HMFO product produced by the process of the present invention achieves an LS HMFO product (i.e., 0.5 wt% sulfur content) having the bulk properties of ISO 8217:2017 compliant RMK-500 residual fuel oil. It will also be understood that the process can be successfully carried out under non-hydrocracking conditions (i.e., low temperature and pressure) that significantly reduce the hydrocracking of the raw materials. Furthermore, when the conditions were increased to even higher pressure (Example E), a product with a lower sulfur content was obtained, but an increase in the production of light hydrocarbons and crude naphtha was observed.

[0116] Those skilled in the art will understand that the exemplary embodiments described above can be modified without departing from the broader concept of the invention. Therefore, it will be understood that the disclosed concept of the invention is not limited to the disclosed exemplary embodiments or examples, but is intended to include modifications within the scope of the concept of the invention as described in the claims.

Claims

1. A low-sulfur marine heavy fuel oil essentially derived from high-sulfur marine heavy fuel oil that has been subjected to hydrodesulfurization and hydrodemetallation reaction conditions and 100% hydrogenated, The above-mentioned high-sulfur marine heavy fuel oil conforms to ISO 8217:2017 as marine residual fuel oil before hydrogenation, but contains environmental pollutants and has a sulfur concentration exceeding 0.5% by weight. Environmental pollutants are (i) Contains sulfur, or (ii) In addition to sulfur, one or more selected from the group consisting of vanadium, nickel, iron, aluminum, silicon, and combinations thereof, The above low-sulfur heavy marine fuel oil conforms to ISO 8217:2017 as marine residual fuel oil, possesses suitable quality as marine residual fuel oil, has a sulfur concentration of less than 0.5% by weight, a vanadium content of less than 450 mg / kg, or a total aluminum and silicon content of 60 mg / kg or less.

2. The sulfur content is determined according to ISO 14596 or ISO 8754. The vanadium content is determined according to IP501, IP470, or ISO14597. The nickel content is determined by IP501 or IP470. The iron content is determined by IP501 or IP470. The aluminum content is determined according to IP501, IP470, or ISO10478. The silicon content is determined by IP501, IP470, or ISO10478. Low-sulfur heavy fuel oil for marine use as described in claim 1.

3. The above-mentioned high-sulfur marine heavy fuel oil has a sulfur content in the range of 1.0% to 5.0% by weight, as determined by ISO 14596 or ISO 8754, and a kinematic viscosity at 50°C of 180 mm², as determined by ISO 3104. ２ / sec ~ 700mm ２ The range is per second, and the density at 15°C, as determined by ISO 3675, is 991.0 kg / m³. ３ ~1010.0kg / m ３ The low-sulfur marine heavy fuel oil according to claim 1 or 2, wherein the CCAI is in the range of 780 to 870 and the flash point determined by ISO 2719 is 60.0°C or higher.

4. A low-sulfur hydrocarbon fuel composition essentially consisting of a large volume of hydrogenated and hydrodesulfurized high-sulfur marine residue fuel oil and a small volume of diluent, wherein the high-sulfur marine residue fuel oil is hydrogenated under hydrogenated and hydrodesulfurization reaction conditions, but the hydrocracking does not exceed 10% of the total mass balance. The above-mentioned high-sulfur marine residual fuel oil conforms to ISO 8217:2017 as marine residual fuel oil before hydrogenation, but contains environmental pollutants and has a sulfur concentration exceeding 0.5% by weight. Environmental pollutants are (i) Contains sulfur, or (ii) In addition to sulfur, one or more selected from the group consisting of vanadium, nickel, iron, aluminum, and silicon, The above low-sulfur hydrocarbon fuel composition conforms to ISO 8217:2017 as marine residual fuel oil, has a sulfur concentration of less than 0.5% by weight, and has a vanadium content of less than 450 mg / kg or a total aluminum and silicon content of 60 mg / kg or less. The above-mentioned diluent is a low-sulfur hydrocarbon fuel composition selected from the group consisting of hydrocarbon materials, non-hydrocarbon materials, solid materials, and combinations thereof.

5. The concentrations of the above environmental pollutants are based on the following criteria: Sulfur is defined in ISO 14596 or ISO 8754. Vanadium is IP501, IP470, or ISO14597. Silicon is IP501, IP470, or ISO10478. Nickel is IP501 or IP470. Iron is IP501 or IP470 The low-sulfur hydrocarbon fuel composition according to claim 4, determined by...

6. The above-mentioned high-sulfur marine residual fuel oil has a sulfur content in the range of 1.0% to 5.0% by weight, as determined by ISO 14596 or ISO 8754, and a kinematic viscosity at 50°C of 180 mm², as determined by ISO 3104. ２ / sec ~ 700mm ２ The range is per second, and the density at 15°C, as determined by ISO 3675, is 991.0 kg / m³. ３ ~1010.0kg / m ３ The low-sulfur hydrocarbon fuel composition according to claim 4 or 5, wherein the CCAI is in the range of 780 to 870 and the flash point determined by ISO 2719 is 60.0°C or higher.

7. The above low-sulfur hydrocarbon fuel composition has a sulfur content determined by ISO 14596 or ISO 8754 of less than 0.5% by weight, a kinematic viscosity at 50 °C determined by ISO 3104 of 180 mm ２ / s to 700 mm ２ / s, a density at 15 °C determined by ISO 3675 of 991.0 kg / m ３ to 1010.0 kg / m ３ in the range, a CCAI in the range of 780 - 870, a flash point determined by ISO 2719 of 60.0 °C or higher, a total sediment due to aging determined by ISO 10307-2 of less than 0.10% by weight, and a residual carbon content by the micro method determined by ISO 10370 in the range of 18.00% to 20.00% by weight, the low-sulfur hydrocarbon fuel composition according to any one of claims 4 to 6.

8. A marine heavy fuel oil product that conforms to ISO 8217:2017 as marine residual fuel, possesses suitable quality as marine heavy fuel oil, contains environmental pollutants, and has a sulfur concentration of less than 0.5% by weight, The above environmental pollutants are (i) Contains sulfur, or (ii) In addition to sulfur, one or more selected from the group consisting of vanadium, nickel, iron, aluminum, silicon, and combinations thereof, The above marine heavy fuel oil products have undergone hydrodemetallation and hydrodesulfurization, but have not been substantially hydrocracked. Marine heavy fuel oil products manufactured by a process including the following steps a) to f): a) A process of obtaining a raw material mixture by combining a predetermined amount of marine heavy fuel oil with a predetermined amount of activated gas, The above-mentioned heavy marine fuel oil has bulk properties that conform to ISO 8217:2017 as marine residual fuel oil, but contains environmental pollutants and has a sulfur concentration exceeding 0.5% by weight, b) A step of processing the above raw material mixture under predetermined temperature and pressure conditions to obtain a heated and pressurized raw material mixture. c) The heated and pressurized raw material mixture is subjected to reaction conditions that are suitable for hydrogenation and hydrogenation and desulfurization, and under which hydrocracking accounts for less than 10% by weight of the total material balance. A process mixture is obtained by contacting one or more catalyst systems selected from the group consisting of a boiling bed-supported transition metal heterogeneous catalyst, a stationary bed-supported transition metal heterogeneous catalyst, and a combination of a boiling bed-supported transition metal heterogeneous catalyst and a stationary bed-supported transition metal heterogeneous catalyst in a reaction vessel, The above process mixture includes a liquid hydrocarbon component, a by-product hydrocarbon component, a bulk gas component, and a residual gas component, in the process, d) A step of releasing the process mixture from contact with the one or more catalyst systems in the at least one reaction vessel, transferring the process mixture from the at least one reaction vessel to at least one second vessel by fluid communication, and separating the liquid hydrocarbon component, by-product hydrocarbon component, and residual gas component of the process mixture from the bulk gas component of the process mixture. e) A step of transferring the liquid hydrocarbon component, by-product hydrocarbon component, and residual gas component separated from the bulk gas component of the process mixture from the at least one second vessel to at least one third reaction vessel by fluid communication, thereby separating the liquid hydrocarbon component of the process mixture from the residual gas component and the by-product hydrocarbon component to obtain the marine heavy fuel oil product, and f) A step of discharging the marine heavy fuel oil product from at least one third reaction vessel.

9. Sulfur is determined according to ISO 14596 or ISO 8754. Vanadium is determined by IP501, IP470, or ISO14597. Nickel is determined by IP501 or IP470. Iron is determined by IP501 or IP470. Aluminum is determined by IP501, IP470, or ISO10478. Silicon is determined by IP501, IP470, or ISO10478. A product obtained by the process described in claim 8.

10. The above process further includes mixing the large amount of marine heavy fuel oil product discharged in step f) with a small amount of diluent selected from hydrocarbon materials, non-hydrocarbon materials, solid materials, and combinations thereof. A product obtained by the process described in claim 8 or 9.

11. The above catalyst system is selected from the group consisting of hydrogenation desulfurization catalysts, hydrogenation transition catalysts, hydrogenation demetallation catalysts, and combinations thereof, and does not have substantial hydrogen cracking performance. The above catalyst system consists of a porous inorganic oxide catalyst support selected from the group consisting of alumina, alumina / boria support, support containing metal-containing aluminosilicate, alumina / phosphorus support, alumina / alkaline earth metal compound support, alumina / titania support, and alumina / zirconia support, impregnated with one or more transition metal components selected from the group consisting of groups 6, 8, 9, and 10 of the periodic table, and then sulfided after impregnation. A product obtained by the process described in any one of claims 8 to 10.

12. The above catalyst system includes one or more fixed-bed supported heterogeneous transition metal catalysts selected from the group consisting of hydrogenation demetallation catalysts, hydrogenation transition catalysts, hydrogenation desulfurization catalysts, and combinations thereof. The above-mentioned supported transition metal heterogeneous catalyst consists of a catalyst support selected from the group consisting of alumina, alumina / boria support, support containing metal-containing aluminosilicate, alumina / phosphorus support, alumina / alkaline earth metal compound support, alumina / titania support, and alumina / zirconia support, impregnated with a mixture of transition metals selected from Ni-Mo, Co-Mo, Ni-W, and Ni-Co-Mo, and then sulfided after impregnation. A product obtained by the process described in any one of claims 8 to 11.

13. The ratio of activated gas to marine heavy fuel oil raw material is in the range of 2500 scf / bbl for HMFO raw material to 4500 scf / bbl for marine heavy fuel oil raw material. A product obtained by the process described in any one of claims 8 to 12.

14. In at least one of the above reaction vessels, The reaction temperature conditions are 650°F to 850°F. The pressure response conditions are 1000 psig to 2500 psig. The reaction conditions for the liquid space velocity are 0.08 / hour to 0.5 / hour. A product obtained by the process described in any one of claims 8 to 13.

15. In at least one of the above reaction vessels, the hydraulic capacity rate is such that the marine heavy fuel oil feedstock is 5,000 bbl / day to 45,000 bbl / day. A product obtained by the process described in claim 13 or 14.

16. A low-sulfur marine heavy fuel oil essentially derived from high-sulfur marine heavy fuel oil that has been hydrogenated under conditions of hydrodesulfurization and hydrodemetallation, and under conditions in which hydrocracking accounts for less than 10% by weight of the total mass balance, wherein the high-sulfur marine heavy fuel oil conforms to ISO 8217:2017 as marine residual fuel oil, except that the sulfur content (ISO 14596 or ISO 8754) exceeds 0.5% by weight before hydrogenation. The above low-sulfur heavy marine fuel oil conforms to ISO 8217:2017 as marine residual fuel oil, possesses suitable quality as marine residual fuel oil, and has a sulfur content (ISO 14596 or ISO 8754) of less than 0.5% by weight. The above-mentioned low-sulfur marine heavy fuel oil has a vanadium content of less than 450 mg / kg or a total aluminum and silicon content of 60 mg / kg or less. Low sulfur marine heavy fuel oil.

17. The low-sulfur heavy fuel oil for marine use according to claim 16, wherein the sulfur content (ISO 14596 or ISO 8754) of the high-sulfur heavy fuel oil for marine use is in the range of 1.0% by weight to 5.0% by weight, and the sulfur content (ISO 14596 or ISO 8754) of the low-sulfur heavy fuel oil for marine use is in the range of 0.5% by weight to 0.05% by weight.

18. The low-sulfur heavy fuel oil for marine use according to claim 16 or 17, wherein the sulfur content (ISO 14596 or ISO 8754) of the low-sulfur heavy fuel oil for marine use is less than 0.1% by weight.

19. A low-sulfur hydrocarbon fuel composition consisting essentially of a large volume of high-sulfur marine residue fuel oil and a small volume of diluent, which have been hydrogenated under conditions of hydrodesulfurization and hydrodemetallation, and under conditions in which hydrocracking accounts for less than 10% by weight of the total mass balance, High-sulfur marine heavy fuel oil conforms to ISO 8217:2017 as marine residual fuel oil, except that its sulfur content (ISO 14596 or ISO 8754) exceeds 0.5% by weight before hydrotreatment. The above low-sulfur hydrocarbon fuel composition conforms to ISO 8217:2017 as marine residual fuel oil, and has a sulfur content (ISO 14596 or ISO 8754) of less than 0.5% by weight. The above diluent is selected from the group consisting of hydrocarbon materials, non-hydrocarbon materials, solid materials, and combinations thereof. The above low-sulfur hydrocarbon fuel composition conforms to ISO 8217:2017. The above low-sulfur hydrocarbon fuel composition has a vanadium content of less than 450 mg / kg or a total aluminum and silicon content of 60 mg / kg or less. Low-sulfur hydrocarbon fuel composition.

20. The composition according to claim 19, wherein the hydrogenated high-sulfur marine residual fuel oil is at least 75% by volume of the low-sulfur hydrocarbon fuel composition, and the diluent is 25% by volume or less of the low-sulfur hydrocarbon fuel composition.

21. The composition according to claim 19 or 20, wherein the hydrogenated high-sulfur marine residual fuel oil is at least 90% by volume of the composition, and the diluent is 10% by volume or less of the composition.

22. The above hydrocarbon materials include marine heavy fuel oil with a sulfur content (ISO 14596 or ISO 8754) exceeding 0.5% by weight; distillate fuels; diesel; light oil; marine light oil; marine diesel oil; cutter oil; biodiesel; methanol, ethanol; synthetic hydrocarbons and oils based on gas liquefaction technology; Fischer-Tropsch oil; synthetic oils based on polyethylene, polypropylene, dimers, trimers and polybutylene; atmospheric residue; vacuum residue; flow Dynamic catalytic cracking (FCC) slurry oil; FCC cycle oil; pyrolytic diesel fuel; cracked light diesel fuel (CLGO); cracked heavy diesel fuel (CHGO); light cycle oil (LCO); heavy cycle oil (HCO); pyrolytic residue; heavy coker distillate; bitumen; heavy deasphaltized oil; visbreaker residue; slop oil; asphalt oil; used or recycled motor oil; lubricating oil aromatic extracts; crude oil; heavy crude oil; distressed crude oil; and combinations thereof. The composition according to any one of claims 19 to 21, wherein the non-hydrocarbon material is selected from the group consisting of residual water; detergents; viscosity modifiers; pour point depressants; lubricity modifiers; haze removers; defoamers; ignition enhancers; rust inhibitors; corrosion inhibitors; wear-resistant additives, antioxidants (phenol compounds and derivatives, etc.), coating agents and surface modifiers, metal deactivators, antistatic agents, ionic and nonionic surfactants, stabilizers, cosmetic colorants and deodorizers, and combinations thereof, and the solid material is selected from the group consisting of carbon or hydrocarbon solids; coke; graphite solids; finely aggregated asphaltenes, iron rust; oxidative corrosion solids; bulk metal particles; paint particles; surface coating particles; plastic particles or polymer particles or elastomer particles, rubber particles; catalyst fine particles; ceramic particles; mineral particles; sand; clay; soil particles; microorganisms; biologically produced solids; and combinations thereof.

23. Low-sulfur marine fuel oil essentially consisting of a product obtained by a method including the following steps: A process to obtain a raw material mixture by mixing a predetermined amount of heavy marine fuel oil, which conforms to ISO 8217:2017 as marine residual fuel oil except that the sulfur content exceeds 0.5% by weight, with a predetermined amount of activated gas. A process mixture is obtained by contacting the above raw material mixture with one or more catalyst systems selected from the group consisting of a fixed-bed supported transition metal heterogeneous catalyst, a boiling-bed supported transition metal heterogeneous catalyst, an inactive catalyst material, and combinations thereof, in a reaction process under hydrodesulfurization and hydrodemetallation reaction process conditions in which hydrocracking accounts for less than 10% by weight of the total mass balance, in at least one reaction vessel. A step of releasing the above process mixture from contact with the one or more catalyst systems in the at least one reaction vessel. A step of transferring the above process mixture from at least one reaction vessel to at least one gas-liquid separation vessel by fluid communication, A step of separating the above process mixture into a liquid component and a gaseous component in at least one gas-liquid separation container. A step of transferring the liquid component of the above process mixture from the at least one gas-liquid separation vessel to the at least one hydrocarbon fractional distillation vessel by fluid communication, A step of separating the low-sulfur marine fuel oil component from the liquid component of the above process mixture, and A step of discharging the above-mentioned low-sulfur marine fuel oil components as low-sulfur marine fuel oil from at least one hydrocarbon fractionation vessel, wherein the low-sulfur marine fuel oil is not further processed and conforms to ISO 8217:2017 as marine residual fuel oil.

24. The low-sulfur marine fuel oil according to claim 23, wherein the sulfur content (ISO 14596 or ISO 8754) of the above-mentioned heavy marine fuel oil is in the range of 1.0% by weight to 5.0% by weight, and the sulfur content (ISO 14596 or ISO 8754) of the above-mentioned low-sulfur marine fuel oil is in the range of 0.5% by weight to 0.05% by weight.

25. The low-sulfur marine fuel oil according to claim 23 or 24, wherein the sulfur content (ISO 14596 or ISO 8754) of the low-sulfur marine fuel oil is less than 0.1% by weight.

26. The above method, The present invention further includes step i) obtaining a low-sulfur marine fuel composition conforming to ISO 8217:2017 as marine residual fuel oil by blending at least 75% by volume of the above low-sulfur marine fuel oil conforming to ISO 8217:2017 with 25% by volume or less of a diluent, Low-sulfur marine fuel oil according to any one of claims 23 to 25.

27. The above diluent is selected from the group consisting of hydrocarbon materials, non-hydrocarbon materials, solid materials, and combinations thereof. Furthermore, the above hydrocarbon material is a marine heavy fuel oil with a sulfur content (ISO 14596 or ISO 8754) exceeding 0.5% by weight; distillate fuels; diesel; light oil; marine light oil; marine diesel oil; cutter oil; biodiesel; methanol, ethanol; synthetic hydrocarbons and oils based on gas liquefaction technology; Fischer-Tropsch oil; synthetic oils based on polyethylene, polypropylene, dimers, trimers, and polybutylene; atmospheric pressure Low-sulfur marine fuel oil according to claim 26, selected from the group consisting of residual oil; vacuum residual oil; fluid catalytic cracking (FCC) slurry oil; FCC cycle oil; pyrolysis diesel oil; cracked light diesel oil (CLGO); cracked heavy diesel oil (CHGO); light cycle oil (LCO); heavy cycle oil (HCO); pyrolysis residual oil; heavy coker distillate oil; bitumen; heavy deasphalt oil; visbreaker residual oil; slop oil; asphalt oil; used or recycled motor oil; lubricating oil aromatic extract; crude oil; heavy crude oil; distressed crude oil; and combinations thereof.

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