heavy marine fuel oil composition

专利摘要:
a process to reduce environmental contaminants in a feed sea heavy marine fuel oil according to iso 8217 (feed load), the process involving: mixing an amount of the feed load with an amount of activating gas mixture to give a mixture feed load; contacting the feed charge mixture with one or more catalysts to form a process mixture from the feed charge mixture; separating the liquid components of the heavy product (product) marine fuel oil from the process mixture from the gaseous components and by-product hydrocarbon components of the process mixture and discharging the product. the product complies with iso standards for residual marine fuel oils and has a sulfur level in the range of 0.05% by weight to 0.50% by weight. the product can be used as such or as a blend filler for conformity, heavy low sulfur or ultra low sulfur marine fuel oil. a device for conducting the process is also revealed.
公开号:BR112019016659A2
申请号:R112019016659
申请日:2018-02-12
公开日:2020-04-07
发明作者:R Klussman Bertrand；J Moore Michael
申请人:Magema Tech Llc；
IPC主号:

专利说明:

COMPOSITION OF HEAVY MARITIME FUEL OIL
FUNDAMENTALS [001] There are two types of marine fuel oil, distillate-based marine fuel oil and residual-based marine fuel oil. Distillate-based marine fuel oil, also known as marine diesel oil (MGO) or marine diesel oil (MDO), comprises oil fractions separated from crude oil in a refinery via a distillation process. Diesel (also known as medium diesel) is an oil distillate intermediate in boiling range and viscosity between kerosene and lubricating oil containing a mixture of C10-19 hydrocarbons. Diesel is used for heating homes and is used in heavy equipment, such as cranes, bulldozers, generators, excavators, tractors and combine harvesters. Generally, maximizing the recovery of diesel from waste is the most economical use of materials by refiners, as they can crack diesel fuel into valuable distillates and gasoline. Diesel oils are very similar to diesel oils containing predominantly a mixture of C10-C19 hydrocarbons, which include approximately 64% aliphatic hydrocarbons, 1-2% olefinic hydrocarbons and 35% aromatic hydrocarbons. Marine diesel can contain up to 15% residual process currents and, optionally, up to no more than 5% by volume of polycyclic aromatic hydrocarbons (asphaltenes). Diesel fuels are used primarily as a ground transportation fuel and as a kerosene blend component to form aviation fuel.
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2/57 [002] Residual fuel oils or heavy marine fuel oil (HMFO) comprise a mixture of process residues - fractions that do not boil or vaporize even under vacuum conditions, and have an asphaltene content between 3 and 20 percent by weight. Asphaltenes are large and complex polycyclic hydrocarbons with a propensity to form complex and waxy precipitates. Once asphaltenes have precipitated, they are notoriously difficult to redissolve and are described as fuel tank sludge in the shipping industry and marine fuel supply industry.
[003] Large ocean vessels are dependent on HMFO to power large two-stroke diesel engines for more than 50 years. HMFO is a mixture of aromatics, distillates and residues generated in the crude oil refinery process. Typical currents included in the HMFO formulation include: atmospheric products from tower bottoms (ie, atmospheric residues), vacuum tower bottoms (ie, vacuum residues), viscorreduction residue, FCC light cycle oil (LCO), FCC heavy cycle oil (HCO), also known as FCC funds, FCC mud oil, heavy gas oils and delay cracker oil (DCO), polycyclic aromatic hydrocarbons, recovered land transport engine oils and small portions (smaller than 20% by volume) of cutting oil, kerosene or diesel to obtain the desired viscosity. HMFO has a higher aromatic content than marine distillate fuels noted above. The composition of HMFO is complex and varies with the source of crude oil and refinery processes
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3/57 used to extract the maximum value of a barrel of crude oil. The mixture of components is generally characterized as being viscous, with a high content of sulfur and metal, and a high content of asphaltenes, making HMFO the only product in the refining process that has a lower value per barrel than the crude oil of loading. food.
[004] Industry statistics indicate that about 90% of the HMFO sold contains 3.5% by weight of sulfur. With an estimated total world consumption of HMFO of approximately 300 million tonnes per year, the annual production of sulfur dioxide by the shipping industry is estimated to be above 21 million tonnes per year. Emissions from burning HMFO on ships contribute significantly to both global air pollution levels and local air pollution levels.
[005] MARPOL, the International Convention for the Prevention of Pollution from Ships, as administered by the International Maritime Organization (IMO) was enacted to prevent pollution from ships. In 1997, a new annex was added to MARPOL; the Regulations for the Prevention of Air Pollution from Ships - Annex VI, to minimize emissions suspended in the air from ships (SOx, NOx, ODS, VOC) and their contribution to air pollution. A revised Annex VI, with limits of more stringent emissions was adopted in October 2008, coming into effect in ^the I July 2010 (hereinafter referred to as Annex VI (revised) or simply Annex VI).
[006] MARPOL Annex VI (revised) established a set of strict limits for emissions for operations on ships in designated Emission Control Areas (ECAs).
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The ECAs under MARPOL Annex VI (revised) are: i) Baltic Sea area- as defined in MARPOL Annex - SOx only; ii) North Sea area - as defined in Annex V of MARPOL - SOx only; iii) North America - as defined in Appendix VII of Annex VI of MARPOL - SOx, NOx and PM; and iv) United States Caribbean Sea area - as defined in Appendix VII of Annex VI of MARPOL - SOx, NOx and PM.
[007] Annex VI (revised) was codified in the United States by the Ship Pollution Prevention Act (APPS). Under the authority of APPS, the United States Environmental Protection Agency (EPA), in consultation with the United States Coast Guard (USCG), enacted regulations that incorporate, by reference, the full text of MARPOL Annex VI (revised ). See 40 CFR § 1043.100 (a) (1). I In ^the August 2012, the maximum sulfur content of all marine fuel oils used on board ships operating in US waters / ECA can not exceed 1.00% by weight. (10,000 ppm) and ^the I January 2015, the maximum sulfur content of all marine fuel oils used in areas US ACE was reduced to 0.10 wt% (1,000 ppm). At the time of implementation, the United States government indicated that ship operators should work hard to achieve 0.10% (1,000 ppm) of the American ECA area marine fuel oil sulfur standard. To encourage adherence, EPA and USCG refused to consider the cost of compatible low-sulfur fuel oil as a valid basis for claiming that compatible fuel oil was not available for purchase. Over the past five years, there has been a very strong economic incentive to meet the demands of
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5/57 marine industry for a low sulfur HMFO, however, technically viable solutions have not been realized. There is an ongoing and urgent demand for processes and methods for the production of a low sulfur HMFO that complies with MARPOL emission requirements - Annex VI.
[008] Due to the ECA areas, all ocean vessels that operate both inside and outside these ECA areas must operate with different marine fuel oils to meet their limits and achieve maximum economic efficiency. In such cases, before entering the ECA area, a ship must switch entirely to the use of ECA-compatible marine fuel oil, and that has written procedures implemented on board on how this should be done. Similarly, changing the use of fuel oil compatible with ECA and back to HMFO should not begin before leaving the ECA area. With each change, it is required that the quantities of fuel oils in accordance with the ECA area on board are recorded, with the date, time and position of the ship when either completing the change before entering or starting the change after leaving such areas . These records must be made in a logbook, as prescribed by the State of the ship's flag, in the absence of any specific requirements that the record can be made, for example, in Annex I of the ship's Oil Record Book.
[009] Annex VI (revised) also sets global limits for sulfur oxide and nitrogen oxide emissions from ship exhausts and particulate matter and prohibits deliberate emissions of substances
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6/57 depleting the ozone layer, such as hydrochlorofluorocarbons. Under the revised MARPOL Annex VI, the overall limit for sulfur HMFO was reduced to 3.50% by weight, from ^the I January 2012; then was further reduced to 0.50%, to take effect from ^the I January 2020. This regulation has been the subject of much discussion both in the maritime shipping industry and in the supply of marine fuels. Under the global limit, all vessels must use HMFO with a sulfur content of not more than 0.50% by weight. IMO has repeatedly indicated to the ocean transportation sector, despite the availability of compliant fuel and the price of fuel compatible, adherence to the sulfur limit of 0.50% by weight for HMFO occur in ^the I January 2020 and IMO expects the fuel oil market to address this requirement. There was a very strong economic incentive to meet the demands of the international maritime industry for low sulfur HMFO, however, technically viable solutions were not achieved. There is a continuous and urgent demand for processes and methods for the production of a low sulfur HMFO that complies with the MARPOL Annex VI emission requirements.
[0010] IMO Regulation 14 establishes both the limit values and the means for their compliance. These can be divided into methods called primary (in which the formation of the pollutant is avoided) or secondary (in which the pollutant is formed, but removed before the exhaust gas is discharged into the atmosphere). There are no guidelines for any primary methods (which could
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7/57 include, for example, mixing on board liquid fuel oils or dual fuel (use of gas / liquid)). In secondary control methods, guidelines (MEPC.184 (59)) were adopted for exhaust gas cleaning systems; when using such arrangements, there would be no restriction on the sulfur content of fuel oils as supplied by bunkers, other than that given by the system certification. For numerous technical and economic reasons, secondary controls were rejected by the major shipping companies and were not widely adopted in the shipping industry. The use of secondary controls is not seen as a practical solution by the shipping industry.
[0011] Primary control solutions: One point for adhering to MARPOL requirements has focused on primary control solutions to reduce sulfur levels in marine fuel components prior to combustion, based on the replacement of HMFO with alternative fuels. However, the shift from HMFO to alternative fuels poses a number of problems for ship operators, many of which are not yet understood by the shipping industry or the refining industry. Due to the potential risks to the ship's propulsion systems (eg fuel systems, engines, etc.), when a ship changes fuel, the conversion process must be done safely and effectively to avoid any technical problems. However, each alternative fuel has economic and technical difficulties to adapt to decades of HMFO-based transportation infrastructure and supply systems used by the transportation industry.
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8/57 maritime.
[0012] LNG: The most prevalent primary control solution in the maritime industry is the adoption of LNG as a primary fuel or additive for HMFO. An increasing number of ships are using liquefied natural gas (LNG) as a primary fuel. Natural gas as a marine fuel for combustion turbines and diesel engines leads to negligible sulfur oxide emissions. The benefits of natural gas were recognized in the development by the IMO of the International Ship Code using gases and other low-flash point fuels (the IGF Code), which was adopted in 2015. However, LNG presents the shipping industry with operational challenges including : storage on board a cryogenic liquid in a marine environment will require extensive renovation and replacement of bunker fuel storage systems and ship fuel transfer; the supply of LNG is far from always present in the main world ports; Up-to-date qualifications and training of the crew to operate LNG or dual-fuel engines will be required before going to sea.
[0013] Sulfur-free biofuels: Another primary solution proposed to achieve compliance with MARPOL requirements is the replacement of HMFO with sulfur-free biofuels. Biodiesel has achieved limited success in replacing petroleum-derived diesel, but supply remains limited. Methanol has been used in some short sea shipping services in the North Sea ECA areas on ferries and other vessels offshore. The widespread adoption of biofuels, such as biodiesel or methanol, presents
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9/57 many challenges for shipowners and the bunker supply industry. These challenges include: compatibility of the fuel system and adaptation of existing fuel systems will be required; contamination during long-term storage of methanol and biodiesel from water and biological contamination; the calorific power of methanol and biodiesel on a per-ton basis is substantially lower than that of HMFO; and methanol has a high vapor pressure and presents serious instant fire safety problems.
[0014] Substitution of heavy fuel oil with marine diesel or marine diesel: A third proposed primary solution is simply to replace HMFO with marine diesel (MGO) or marine diesel (MDO). The first major difficulty is the restriction in the global supply of distilled materials that constitute more than 90% by volume of MGO and MDO. It is reported that the effective replenishment capacity to produce MGO is less than 100 million metric tons per year, resulting in an annual marine fuel deficit of over 200 million metric tons per year. Refineries not only lack the ability to increase MGO production, they also lack economic motivation, because higher values and higher margins can be obtained from ultra low sulfur diesel fuel for land transport systems (trucks, trains , collective transport systems, heavy construction equipment, etc.).
[0015] Mixture: Another primary solution is the blending of HMFO with fuels containing a lower sulfur content, such as low sulfur marine diesel (0.1% by weight)
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10/57 sulfur) to obtain a product HMFO with a sulfur content of 0.5% by weight. In a direct mixing approach (based on linear mixing), each 1 ton (1000 kg) of HSFO (3.5% sulfur) requires 7.5 tons (7500 kg) of 0.1% MGO or MDO material by weight of sulfur to reach an HMFO sulfur level of 0.5% by weight. One skilled in the fuel mixing technique will immediately understand that the mixture affects the main properties of the HMFO, specifically viscosity and density are substantially altered. In addition, a mixing process can result in a fuel with varying viscosity and density that can no longer meet the requirements of an HMFO.
[0016] Other complications can arise when mixed HMFO is introduced into the bunker supply infrastructure and onboard systems otherwise planned for unmixed HMFO. There is a real risk of incompatibility when the two fuels are mixed. The mixture of a distilled fuel, mainly of paraffinic type (MGO or MDO), with an HMFO having a high aromatic content, is often correlated with the low solubility of asphaltenes. Probably, a mixed fuel will result in the precipitation of asphaltenes and / or highly paraffinic materials from the distilled material, forming an untreatable fuel tank sludge. The sludge from the fuel tank causes clogging of filters and separators, pumps and transfer lines, accumulation of sludge in the storage tanks, seizure in the fuel injection pumps (piston and barrel deposits) and clogged fuel nozzles. Such a risk to the propulsion system
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11/57 primary is not acceptable for a cargo ship in the open ocean.
[0017] Finally, the blending of HMFO with marine distilled products (MGO or MDO) is not economically viable. A mixer will take a high value product (marine diesel with 0.1% sulfur (MGO) or marine diesel (MDO)) and mixing it with 7.5 to 1 with low value HMFO high sulfur to create an HMFO final compatible with IMO / MARPOL (ie low sulfur heavy marine fuel oil 0.5% by weight of sulfur - LSHMFO). LSHMFO is expected to be sold at a lower price per tonne than the value of the two mixing loads alone.
[0018] Residual oil processing. Over the past several decades, the focus of the refining industry's research efforts related to the processing of heavy oils (crude oils, 'unfavorable' oils, residual oils) has been to improve the properties of these low-value refinery process oils to create oils lighter with higher value. The challenge has been that crude oil, 'unfavorable' oil and waste can be unstable and contain high levels of sulfur, nitrogen, phosphorus, metals (especially vanadium and nickel) and asphaltenes. Much of nickel and vanadium is difficult to remove from chelates with porphyrins. Vanadium and nickel porphyrins and other metallic organic compounds are responsible for catalyst contamination and corrosion problems at the refinery. Sulfur, nitrogen and phosphorus are removed because they are well-known poisons for the precious metal catalysts (platinum and palladium) used in the downstream processes of atmospheric or vacuum distillation towers.
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12/57 [0019] The difficulties in treating residual atmospheric or vacuum currents have been known for many years and have been the subject of considerable research and investigation. Numerous waste-oil conversion processes have been developed, in which the objectives are the same: 1) to create a more valuable hydrocarbon product, preferably in the distillate range; and 2) concentrate contaminants such as sulfur, nitrogen, phosphorus, metals and asphaltenes in a form (coke, heavy coke residue, FCC sludge oil) to remove the refinery stream. The well-known and accepted practice in the refining industry is to increase the severity of the reaction (elevated temperature and pressure) to produce lighter and purified hydrocarbon products, increase the life span of the catalyst and remove sulfur, nitrogen, phosphorus, metals and asphaltenes from the refinery chain.
[0020] It is also well known in these processes that the nature of the feed load has a significant influence on the products produced, the useful life of the catalyst and, finally, the economic viability of the process. In a representative technical paper, ResidualOil Hydrotreating Kinetics for Graded Catalyst Systems: Effects of Original and Treated Feedstocks, it is stated that the results revealed significant changes in activity, depending on the feed load used for the tests. The study demonstrates the importance of the proper selection of feed loads used in the performance evaluation and screening of candidate catalyst for graduated catalyst systems for hydrotreating residual oil. From this study, those versed in the art
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13/57 would understand that the conditions required for successful hydroprocessing of atmospheric waste are not applicable for the successful hydroprocessing of vacuum waste that are not applicable for the successful hydroprocessing of viscorreduction waste, and so on. Successful reaction conditions depend on the feed load. For this reason, modern and complex refineries have multiple hydroprocessing units, each unit being directed to a specific hydrocarbon stream with a focus on creating desirable and valuable light hydrocarbons and providing an acceptable product for the next downstream process.
[0021] An additional difficulty in processing heavy oil residues and other heavy hydrocarbons is the inherent instability of each intermediate refinery stream. One skilled in the art understands that there are many practical reasons for each refinery chain to be handled in isolation. One of these reasons is the unpredictable nature of the asphaltenes contained in each stream. Asphalts are large and complex hydrocarbons with a propensity to precipitate from the refinery hydrocarbon streams. One skilled in the art knows that even small changes in components or physical conditions (temperature, pressure) can precipitate asphaltenes that were otherwise dissolved in solution. Once precipitated from the solution, asphaltenes can quickly block vital lines, control valves, coat critical sensing devices (ie temperature and pressure sensors) and generally result in severe and very costly interruption and shutdown of a unit
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14/57 or the complete refinery. For this reason, it has been a long-standing practice within refineries not to mix streams of intermediate products (such as atmospheric residue, vacuum residue, FCC sludge oil, etc ...) and process each stream in separate reactors.
[0022] In summary, since the announcement of MARPOL standards reducing global sulfur levels in HMFO, crude oil refineries have made no technical efforts to create a low sulfur substitute for HMFO. Despite strong government and economic incentives and the needs of the international shipping industry, refineries have little economic reason to deal with removing environmental contaminants from HMFOs. Instead, the global refining industry has focused on generating higher yields from each barrel of oil by creating light hydrocarbons (ie, diesel and gasoline) and concentrating environmental contaminants in ever smaller value streams (ie, waste) and products (petroleum coke, HMFO). Shipping companies have focused on short-term solutions, such as installing purification units, or adopting the limited use of more expensive low-sulfur marine diesel and marine gas oils as a substitute for HMFO. In the open sea, most, if not all, of the major shipping companies continue to use the most economically viable fuel, that is, HMFO. An old and unmet need remains for processes and devices that remove environmental contaminants (ie, sulfur, nitrogen, phosphorus, metals especially vanadium and nickel) from HMFO without changing the qualities and
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15/57 properties that make HMFO the most economical and practical way of energizing transoceanic vessels. In addition, there remains a long-term and unmet need for HMFO with low sulfur content (ie 0.5% by weight of sulfur) or ultra low (0.10% by weight of sulfur) in accordance with IMO, which it is also compatible with the raw properties required for a marketable ISO 8217 HMFO.
SUMMARY [0023] It is a general objective to reduce ambient contaminants from heavy marine fuel oil (HMFO) in a process that minimizes changes in desirable HMFO properties and minimizes unnecessary production of hydrocarbon by-products (ie, light hydrocarbons ( Ci-Cs) and wild naphtha (C5-C20).
[0024] A first aspect and illustrative modality encompass a process to reduce environmental contaminants in a feed load heavy marine fuel oil, the process involving: mixing a quantity of feed load heavy marine fuel oil with a mixture amount of activation gas to give a mixture of feed charge; contacting the feed charge mixture with one or more catalysts to form a process mixture from the feed charge mixture; receiving said process mixture and separating the liquid components of the product's heavy marine fuel oil from the process mixture from the gaseous components and hydrocarbon components by-products of the process mixture and discharging the product's heavy marine fuel oil.
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A second aspect and illustrative embodiment encompass a hydrocarbon fuel composition, referred to herein as a heavy marine fuel composition, consisting essentially of at least a greater part by volume, preferably 85% by volume, more preferably by less 90% by volume and most preferably at least 95% by volume of product heavy marine fuel oil resulting from the process described to reduce environmental contaminants in a feed cargo heavy marine fuel oil or optionally produced by devices embodying that process. The rest of the volume in the heavy marine fuel composition can be of diluting materials with the product HMFO, but it does not result in a mixture that does not meet ISO 8217: 2017 standards for the crude properties of residual marine fuels and reaches a content of sulfur below the global standard of 0.5% by weight of sulfur MARPOL (ISO 14596 or ISO 8754).
[0026] A third aspect and illustrative modality encompass a device to reduce environmental contaminants in a feed charge HMFO and produce a product HMFO. The illustrative device comprises a first vessel, a second vessel in fluid communication with the first vessel and a third vessel in fluid communication with the second vessel and a discharge line from the third vessel to discharge the product HMFO. The first vessel receives an amount of feed charge HMFO mixed with an amount of an activation gas mixture and contacts the resulting mixture with one or more catalysts under certain process conditions to form
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17/57 a process mix. The second vessel receives the process mixture from the first vessel, separates the liquid components from the crude gas components within the process mixture. The crude gaseous components are sent for further processing. The liquid components are sent to the third vessel to separate any residual gaseous components and any by-product hydrocarbon components (mainly light and wild naphtha) from the processed product HMFO which is subsequently discharged.
DESCRIPTION OF DRAWINGS [0027] Figure 1 is a process flow chart of a process for producing product HMFO.
[0028] Figure 2 is a basic schematic diagram of an installation to produce product HMFO.
DETAILED DESCRIPTION [0029] The inventive concepts as described here use terms that should be well known to those skilled in the art, however, some terms are used having a specific desired meaning and these terms are defined below.
[0030] Heavy marine fuel oil (HMFO) is a petroleum product fuel in accordance with ISO 8217: 2017 for the crude properties of residual marine fuels, except for the concentration levels of environmental contaminants.
[0031] Environmental contaminants are organic and inorganic components of HMFO that result in the formation of SOx, NOx and particulate materials upon combustion.
[0032] Feed load HMFO is a petroleum product fuel in accordance with ISO 8217
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18/57: 2017 for the crude properties of residual marine fuels except for the concentration of environmental contaminants, preferably the feed load HMFO has a sulfur content higher than the global MARPOL standard of 0.5% by weight of sulfur, and preferably and has a sulfur content (ISO 14596 or ISO 8754) in the range of 5.0% by weight to 1.0% by weight.
[0033] Heavy marine fuel composition is a hydrocarbon fuel composition that essentially consists of at least 85% by volume of the HMFO Product and not more than 15% by volume of Diluting Materials and complies with ISO 8217: 2017 for bulk properties of residual marine fuels and a sulfur content lower than the global standard of MARPOL of 0.5% by weight sulfur (ISO 14596 or ISO 8754).
[0034] Diluent materials are hydrocarbon or non-hydrocarbon materials mixed in or combined with or added to and suspended solids in the product HMFO, whose presence does not result in a mixture that fails to meet ISO 8217: 2017 for crude fuel properties marine residues and result in a sulfur content higher than the global MARPOL standard of 0.5% by weight of sulfur (ISO 14596 or ISO 8754).
[0035] Product HMFO is a petroleum product fuel in compliance with ISO 8217: 2017 standards for the crude properties of marine residual fuels and achieves a lower sulfur content than specified in the global 0.5 MARPOL standard % by weight of sulfur (ISO 14596 or ISO 8754), and preferably a maximum sulfur content (ISO 14596 or ISO 8754) in the range of 0.05% by weight at
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1.0% by weight.
[0036] Activation gas: is the mixture of gases used in the process combined with the catalyst to remove environmental contaminants from the feed charge HMFO.
[0037] Fluid communication: is the ability to transfer fluids (or liquid, gas or combinations thereof, which may have solids in suspension) from a first vessel or location to a second vessel or location, this may include connections made by tubes (also called a line), coils, valves, intermediate holding tanks or emergence tanks (also called a drum). Marketable quality: is a quality level for a residual marine fuel oil, so that the fuel is suitable for the common purpose for which it is intended (that is, to serve as a source of residual fuel for a marine vessel) and can be sold commercially and fungible with heavy or residual marine fuel.
[0038] Barrel (bbl): is a standard volumetric measure for oil; 1 barrel = 0.1589873 m ³ ; or 1 barrel = 158.9873 liters; or 1 barrel = 42.00 US liquid gallons.
[0039] Bpd: is an abbreviation for barrel per day.
[0040] SCF: is an abbreviation for standard cubic foot of a gas; a standard cubic foot (at 14.73 psi (pound per square inch) and 60 ° F) is equal to 0.0283058557 standard cubic meter (at 101.325 kPa and 15 ° C).
[0041] The inventive concepts are illustrated in greater detail in the description with reference to the drawings, in which FIGURE 1 shows the process flows in generalized blocks to reduce environmental contaminants in a cargo HMFO
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20/57 of feed and produce a product HMFO according to a first illustrative modality. A predetermined volume of HMFO feed charge (2) is mixed with a predetermined amount of activation gas (4) to give a feed charge mix. The feed load HMFO used generally meets the crude physical properties and some key chemicals for a residual marine fuel oil otherwise compliant with ISO8217: 2017, exclusive of environmental contaminants. More particularly, when the environmental contaminant is sulfur, the sulfur concentration in the feed load HMFO can be in the range of 5.0% by weight to 1.0% by weight. The feed load HMFO must have the raw physical properties of an HMFO in accordance with ISO8217: 2017: a maximum kinematic viscosity at 50 ° C (ISO 3104) between the range of 180 mm ² / sulfur to 700 mm ² / sulfur and a maximum density at 15 ° C (ISO 3675) between the range of 991.0 kg / m ³ to 1010.0 kg / m ³ and CCAI is 780 to 870 and a flash point (ISO 2719) of not less than 60.0 C. Other properties of the feed load HMFO connected with the formation of particulate matter (PM) include: a maximum total sediment - aged (ISO 10307-2) of 0.10% by weight and a maximum carbon residue - micro method (ISO 10370) between the range of 18.00% by weight and 20.00% by weight and a maximum content of aluminum plus silicon (ISO 10478) 60 mg / kg. Potential environmental contaminants, other than sulfur, that may be present in the feed load HMFO with respect to ISO requirements, may include vanadium, nickel, iron, aluminum and silicon, substantially reduced by the process of the present invention. However, a person
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21/57 technicians will appreciate that the vanadium content serves as a general indicator for these other environmental contaminants. In a preferred embodiment, the vanadium content conforms to ISO, so that feed charge MHFO has a maximum vanadium content (ISO 14597) between the range of 350 mg / kg to 450 ppm mg / kg.
[0042] Regarding the properties of the activation gas, the activation gas must be selected from mixtures of nitrogen, hydrogen, carbon dioxide, aerated water, and methane. The gas mixture within the activation gas should have an ideal hydrogen gas partial pressure (ρκ2) greater than 80% of the total pressure of the activation gas mixture (F) and more preferably where the activation gas has a pressure partial hydrogen ideal gas (ρκ2) greater than 95% of the total pressure of the activation gas mixture (F). It will be appreciated by a person skilled in the art that the molar content of the activation gas is another criterion, the activation gas must have a molar fraction of hydrogen in the range between 80% and 100% of total moles of the activation gas mixture, more preferably where the activation gas has a molar fraction of hydrogen between 80% and 99% of the total moles of the activation gas mixture [0043] The feed charge mixture (i.e., feed charge HMFO mixture and gas activation) is brought to the temperature and pressure process conditions and introduced into a first vessel, preferably a reactor vessel, so that the feed charge mixture is then contacted with one or more catalysts (8) to form a mixture process from the feed load mix.
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22/57 [0044] Process conditions are selected so that the ratio of the amount of activation gas to the amount of feed charge HMFO is 250 scf gas / barrel (7.07921 m ³ / 158.987 L) of HMFO feed load at 10,000 scf gas / barrel (283,1685 m ³ / 158,987 L) of feed load HMFO; and preferably between 2000 scf gas / barrel (56, 63 369 ^m3 / 158, G 987) of feedstock HMFO; 1 to 5,000 gas scf / bbl (0.0283168 to 141.5842 ^m3 / 158, G 987) of feedstock HMFO more preferably between 2500 gas scf / bbl ^(m3 70.79212 / 158 987 L) Feed load HMFO at 4500 scf gas / barrel (127.4258 m ³ / 158.987 L) feed load HMFO. Process conditions are selected so that the total pressure in the first vessel is between 250 psig (1.72 MPa (g)) and 3000 psig (20.68 MPa (g)); preferably between 1000 psig (6.89 MPa (g)) and 2500 psig (17.23 (MPa (g)), and more preferably between 1500 psig (10.34 (MPa (g)) and 2200 psig (15.2 (MPa (g)). Process conditions are selected so that the temperature indicated within the first vessel is between 500 ° F (260 ° C) to 900 ° F (482 ° C), preferably between 650 ° F (343 ° C) and 850 ° F (454 ° C) and more preferably between 680 ° F (360 ° C) and 800 ° F (426 ° C) .The process conditions are selected so that the hourly spatial speed of liquid within of the first vessel is between 0.05 oil / hour / m ³ catalyst and 1.0 oil / hour / m ³ catalyst, preferably between 0.08 oil / hour / m ³ catalyst and 0.5 oil / hour / m ³ catalyst and more preferably between 0.1 oil / hour / m ³ catalyst and 0.3 oil / hour m ³ catalyst to obtain a desulfurization with product sulfur levels below 0.5% by weight.
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23/57 [0045] A person skilled in the art will appreciate that process conditions are determined to account for the hydraulic capacity of the unit. The exemplary hydraulic capacity for the treatment unit can be between 100 barrels (15898.7 L) of feed load HMFO / day and 100,000 barrels (15898729 L) of feed load HMFO / day, preferably between 1000 barrels (158987 L) feed load HMFO / day and 60,000 barrels (9539237.7 L) feed load HMFO / day, more preferably between 5,000 barrels (794,936 L) feed load HMFO / day and 45,000 barrels (7154 , 43 L) of feed load HMFO / day, and even more preferably between 10,000 barrels (1589873 L) of feed load HMFO / day and 30,000 barrels (4769618.8 L) of feed load HMFO / day [ 0046] The process may use one or more catalyst systems selected from the group consisting of: a heterogeneous transition metal catalyst supported on a boiling bed, a heterogeneous transition metal catalyst supported on a fixed bed, and a combination of heterogeneous catalysts transition metal supported on boiling bed and heterogeneous transition metal catalysts supported on fixed bed. A person skilled in the art will appreciate that a heterogeneous transition metal catalyst supported on a fixed bed will be technically easier to implement and is preferred. The heterogeneous transition metal catalyst comprises a porous inorganic oxide catalyst carrier and a transition metal catalyst. The porous inorganic oxide catalyst carrier is at least one carrier selected from the group
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24/57 consisting of alumina, alumina / barium carrier, a metal-containing aluminosilicate carrier, alumina / phosphorus carrier, alumina carrier / alkaline earth metal compound, alumina / titania carrier and alumina / zirconia carrier. 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 and illustrative embodiment, the heterogeneous transition metal catalyst is a porous inorganic oxide catalyst carrier and a transition metal catalyst, wherein the preferred porous inorganic oxide catalyst carrier is alumina and the preferred metal catalyst transition is Ni — Mo, Co— Mo, Ni — W or Ni-Co — Mo.
[0047] The process mixture (10) is removed from the first vessel (8) and from being in contact with one or more catalysts and is sent via fluid communication to a second vessel (12), preferably a gas-liquid separator or hot separators and cold separators, to separate the liquid components (14) of the process mixture from the crude gaseous components (16) of the process mixture. The gaseous components (16) are treated beyond the battery limits of the immediate process. These gaseous components may include a mixture of activating gas components and lighter hydrocarbons (mainly methane, ethane and propane, but some wild naphtha) that may have been inevitably formed as part of the hydrocarbon by-products of the process.
[0048] The liquid components (16) are sent via fluid communication to a third vessel (18),
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25/57 preferably a fuel oil product extractor system, to separate any residual gaseous components (20) and by-product hydrocarbon components (22) from the product HMFO (24). The residual gaseous components (20) can be a mixture of gases selected from the group consisting of: nitrogen, hydrogen, carbon dioxide, hydrogen sulfide, aerated water, C1-C5 light hydrocarbons. This residual gas is treated outside the limits of the immediate process battery, combined with other gaseous components (16) removed from the process mixture (10) in the second vessel (12). The liquid by-product hydrocarbon component, which are condensable hydrocarbons inevitably formed in the process (22), can be a mixture selected from the group consisting of hydrocarbons C5-C20 (wild naphtha) (naphtha - diesel) and other light condensable liquid hydrocarbons (C4- C8) that can be used as part of the engine fuel mixing tank or sold as gasoline and diesel mixing components on the open market.
[0049] As a side note, the residual gaseous component is a mixture of gases selected from the group consisting of: nitrogen, hydrogen, carbon dioxide, hydrogen sulfide, aerated water, light hydrocarbons. An amine scrubber will effectively remove the hydrogen sulfide content which can then be processed using technologies and processes well known to those skilled in the art. In a preferred illustrative embodiment, hydrogen sulfide is converted to elemental sulfur using Claus' well-known process. An alternative modality uses a registered process for converting sulfide from
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26/57 hydrogen in hydro-sulfuric acid. Either way, sulfur is removed from entering the environment before the HMFO is burned in a ship's engine. The clean gas can be vented, burned or, more preferably, recycled back for use as activation gas.
[0050] The by-product hydrocarbon components are a mixture of C5-C20 hydrocarbons (wild naphtha) (naphtha - diesel) that can be directed to the engine's fuel mix tank or sold, inappropriately, to an adjacent refinery or even used to burn heaters and combustion turbines to provide heat and power to the process. These hydrocarbon by-products which are the result of hydrocracking reactions must be less than 10% by weight, preferably less than 5% by weight and more preferably less than 2% by weight of the rest of the overall process mass.
[0051] The product HMFO (24) is discharged via fluid communication in storage tanks beyond the limits of the immediate process battery.
[0052] Product HMFO - The product HFMO resulting from the illustrative process described is of marketable quality for sale and use as a heavy marine fuel oil (also known as residual marine fuel oil or heavy bunker supply fuel) and displays the properties crude physics required for the product HMFO to be a residual marine fuel oil in accordance with ISO (ie ISO8217: 2017) exhibiting the crude properties: a maximum kinematic viscosity at 50C (ISO 3104) between the 180 mm range ² / sulfur at 700 mm ² / sulfur; maximum density at 15 ° C (ISO 3675) between the
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27/57 range from 991.0 kg / m ³ to 1010.0 kg / m ³ ; a CCAI is in the range of 780 to 870; a flash point (ISO 2719) not less than 60.0 ° C; a maximum total - aged sediment (ISO 103072) of 0.10% by weight; a maximum carbon residue - micro method (ISO 10370) between the range of 18.00% by weight and 20.00% by weight and a maximum content of aluminum plus silicon (ISO 10478) of 60 mg / kg.
[0053] The product HMFO has a sulfur content (ISO
14596 or ISO 8754) smaller than what 0.5% in weight and preferably smaller than 0.1% by weight and more preferably smaller than 0.05 % by weight and is
Completely in accordance with the requirements of Annex IMO VI (revised) for a low sulfur HMFO and preferably an ultra low sulfur HMFO. That is, the sulfur content of the product HMFO has been reduced by about 90% or more when compared to the feed charge HMFO. Similarly, the vanadium content (ISO 14597) of the product's heavy marine fuel oil is less than 10% and more preferably less than 1% of the maximum vanadium content of the feed load heavy marine fuel oil. One skilled in the art will appreciate that a substantial reduction in the sulfur and vanadium content of the feed charge HMFO indicates a process having achieved a substantial reduction in environmental contaminants from the feed load HMFO; of equal importance is that this was achieved while maintaining the desirable properties of an HMFO in accordance with ISO 8217: 2017.
[0054] The product HMFO not only complies with ISO8217: 2017 (and is marketable as a residual marine fuel oil or
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28/57 bunker supply), but the product HMFO has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05% by weight to 1.0% by weight, preferably a sulfur content (ISO 14596 or ISO 8754) between the range of 0.05% by weight ppm and 0.5% by weight and, more preferably, a sulfur content (ISO 14596 or ISO 8754) between the range of 0.1% by weight and 0.05% by weight. The vanadium content of the product HMFO is well within the maximum vanadium content (ISO 14597) required for an ISO8217: 2017 residual marine fuel oil exhibiting a vanadium content of less than 450 ppm mg / kg, preferably a vanadium content ( ISO 14597) less than 300 mg / kg and more preferably a vanadium content (ISO 14597) between the range of 50 mg / kg and 100 mg / kg.
[0055] A specialist in the art of mixing marine fuel blends, bunker fuel formulations and fuel logistics requirements for marine transportation fuels will readily understand that, without further changes in composition or blend, the product HMFO can be sold and used as a low sulfur heavy (residual) marine fuel oil in accordance with MARPOL Annex VI which is a direct substitute for high sulfur heavy (residual) marine fuel oil or fuel supply heavy bunker currently in use. An illustrative embodiment is a low sulfur heavy marine fuel oil in accordance with ISO8217: 2017 comprising (and preferably consisting essentially of) a high sulfur heavy marine fuel oil, 100% hydroprocessed, in accordance with ISO8217: 2017, where the sulfur levels of the oil
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29/57 high sulfur heavy marine fuel, hydroprocessed, in accordance with ISO8217: 2017, are greater than 0.5% by weight and where the sulfur levels of low sulfur heavy marine fuel oil, in according to ISO8217: 2017, are less than 0.5% by weight. Another illustrative embodiment is an ultra-low sulfur heavy marine fuel oil in accordance with ISO8217: 2017 comprising (and preferably consisting essentially of) a high sulfur heavy marine fuel oil, 100% processed in accordance with ISO8217: 2017, where the sulfur levels of the high-sulfur, high-sulfur, heavy marine fuel oil in accordance with ISO8217: 2017 are greater than 0.5% by weight and where the sulfur levels of the heavy marine fuel oil low sulfur content, in accordance with ISO8217: 2017, are less than 0.1% by weight.
[0056] As a result of the present invention, multiple economic and logistical benefits for the bunkering and shipping industries can be achieved. More specifically, the benefits include minimal changes to the existing heavy marine fuel supply infrastructure (storage and transfer systems); minimal changes to on-board systems are necessary to meet the emission requirements of MARPOL Annex VI (revised); no additional training or certifications for crew members will be required, among the realizable benefits. Refining companies will also see multiple economic and logistical benefits, including: there is no need to change or
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30/57 rebalancing refinery operations and product chains to meet a new market demand for low sulfur or ultra low sulfur HMFO; no additional units are needed at the refinery, accompanied by additional capacity for hydrogen or sulfur, because the illustrative process can be conducted as a stand-alone unit; refinery operations can remain centralized in those products that create the most value from the received crude oil (ie production of petrochemicals, gasoline and distillate (diesel); refining companies can continue to use existing slate types of crude oil without having to switch to sweeter or lighter raw materials to meet environmental requirements for HMFO products, to name just a few.
[0057] Heavy marine fuel composition An aspect of the present inventive concept is a fuel composition comprising, but preferably consisting essentially of, the product HMFO resulting from the described processes and, optionally, may include diluent materials. As noted above, the raw properties of the product HMFO itself are in accordance with ISO8217: 2017 and meet the global requirements of IMO Annex VI for the maximum sulfur content (ISO 14596 or ISO 8754). Insofar as ultra-low sulfur levels are desired, the process of the present invention achieves this and one skilled in the marine fuel blending technique will appreciate that a low sulfur or ultra-low sulfur product HMFO can be used as a filler primary blend to form a low sulfur heavy marine fuel composition in
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31/57 the IMO Annex VI. A low sulfur heavy marine fuel composition will comprise (and preferably will consist essentially of): a) the product HMFO and b) diluting materials. In one embodiment, the majority of the volume of the heavy marine fuel composition is the product HMFO, with the rest of the materials being diluent materials. Preferably, the heavy marine fuel composition is at least 75% by volume, preferably at least 80% by volume, more preferably at least 90% by volume and, moreover, preferably at least 95% by volume of HMFO product with the rest being thinner materials.
[0058] Diluent materials can be hydrocarbon-based or non-hydrocarbon-based materials that are mixed in or combined with or added to, or solid particle materials that are suspended in the product HMFO. Diluent materials may intentionally or unintentionally alter the composition of the product HMFO, but not in such a way that the resulting mixture does not comply with ISO 8217: 2017 for the raw properties of residual marine fuels or that does not have a content of sulfur less than the global MARPOL standard of 0.5% by weight of sulfur (ISO 14596 or ISO 8754). Examples of diluent materials that are considered to be hydrocarbon-based materials include: feed charge HMFO (i.e., high sulfur HMFO); distillate-based fuels, such as diesel for roads, diesel, MGO or MDO; cutting oil (currently used in the formulation of residual marine fuel oils); renewable oils and fuels, such as biodiesel, methanol, ethanol and the like;
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32/57 synthetic hydrocarbons and oils based on gas technology for liquids, such as oils derived from FischerTropsch, fully synthetic oils, such as those based on polyethylene, polypropylene, dimer, trimer and poly butylene and the like; refinery waste or other hydrocarbon oils, such as atmospheric residue, vacuum residue, fluid catalytic cracker sludge oil (FCC), FCC cycle oil, pyrolysis diesel, light cracked diesel (CLGO), heavy cracked diesel (CHGO) , light cycle oil (LCO), heavy cycle oil (HCO), thermally cracked residue, heavy coke oven distillate, bitumen, heavy asphalted oil, viscorreduction residue, drainage oils, asphaltene oils; used or recycled motor oils; aromatic extracts of lubricating oils and crude oils such as heavy crude oil, unfavorable crude oils and similar materials that could otherwise be sent to a hydrocracker or diverted to the mixing puddle for a high-grade heavy (residual) marine fuel oil sulfur of the prior art. Examples of diluent materials that are considered to be non-hydrocarbon base materials include: residual water (ie water that is absorbed from moisture in the air or water that is miscible or solubilized, in some cases as microemulsions, in the HMFO hydrocarbons). product), fuel additives that may include, but are not limited to, detergents, viscosity modifiers, drop point depressants, lubricity modifiers, mist removers (for example, alkoxylated phenol formaldehyde polymers), defoaming agents (for example, example, polyether modified polysiloxanes); breeders
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33/57 ignition; anti-rust agents (for example, derivatives of the succinic acid ester); corrosion inhibitors; anti-wear additives, anti-oxidants (for example, phenolic compounds and derivatives), coating agents and surface modifiers, metal deactivators, static dissipating agents, ionic and non-ionic surfactants, stabilizers, colorants and cosmetic odorants and mixtures thereof. A third group of diluting materials may include suspended solids or fine particulate materials that are present as a result of the handling, storage and transportation of the product HMFO or heavy marine fuel composition, including but not limited to: carbon or hydrocarbon solids ( for example, coke, graphite solids or micro-agglomerated asphaltenes), iron rust and other oxidative corrosion solids, fine particles of rough metal, paint particles or surface coating, plastic or polymer particles or elastomer or rubber (for example, resulting from the degradation of joints, valve parts, etc ...), catalyst fines, ceramic or mineral particles, sand, clay and other particles of earth, bacteria and other biologically generated solids, and mixtures of these that may be present as suspended particles, but which do not otherwise affect the marketable quality of the fuel composition heavy marine as a heavy (residual) marine fuel in accordance with ISO 8217: 2017.
[0059] The mixture of product HMFO and diluting materials must be of marketable quality as a heavy marine fuel with a low sulfur content (residual). This is,
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34/57 the blend must be suitable for its intended use as a heavy marine fuel for bunker supply and generally be fungible as bunker fuel for ships sailing in the ocean. Preferably, the heavy marine fuel composition should retain the crude physical properties that are required from a residual marine fuel oil in accordance with ISO 8217: 2017 and a sulfur content lower than the global MARPOL standard of 0.5% by weight of sulfur (ISO 14596 or ISO 8754), so that the material is qualified as low-sulfur heavy marine fuel oil in accordance with MARPOL Annex VI (LS-HMFO). As noted above, the sulfur content of the product HMFO can be significantly less than 0.5% by weight (ie below 0.1% by weight of sulfur (ISO 14596 or ISO 8754)) to qualify as a ultra-low sulfur heavy marine fuel oil (ULS-HMFO) according to Annex VI (revised) MARPOL and a heavy marine fuel composition likewise can be formulated to qualify as an ULS-HMFO in accordance with Annex VI MARPOL, suitable for use as a bunker supply marine fuel in ECA areas. To qualify as an ISO 8217: 2017 qualified fuel, the heavy marine fuel composition of the present invention must meet internationally accepted standards, including: a maximum kinematic viscosity at 50 ° C (ISO 3104) between 180 mm ² / sulfur at 700 mm ² / sulfur; a maximum density at 15 ° C (ISO 3675) between 991.0 kg / m ³ to 1010.0 kg / m ³ ; a CCAI in the range of 780 to 870; a flash point (ISO 2719) of not less than 60.0 ° C; a maximum total of sediments - aged (ISO 10307-2) of 0.10% by weight; a residue
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35/57 maximum carbon - micro method (ISO 10370) between 18.00% by weight and 20.00% by weight and a maximum content of aluminum plus silicon (ISO 10478) of 60 mg / kg.
[0060] Description of production facilities: Turning now to a more detailed illustrative mode of production facilities, Figure 2 shows a scheme for production facilities implementing the process described above to reduce environmental contaminants in a feed load HMFO to produce a product HMFO according to the second illustrative embodiment. An alternative embodiment for the production installation in which multiple reactors are used is within the scope of the present invention and is described in a co-pending description.
[0061] In Figure 2, the feed charge HMFO (A) is fed from the external battery limits (acronym OSBL) to the oil feed emergence drum (1) which receives power from the external battery limits (OSBL ) and provides adequate volume of appearance to ensure smooth operation of the unit. The water entrained in the feed is removed from the HMFO with the water being discharged in a stream (lc) for treatment in the external limits OSBL.
[0062] The feed charge HMFO (A) is removed from the oil feed emergence drum (1) via line (lb) by the oil feed pump (3) and is pressurized at the pressure required for the process. The pressurized HMFO (A ') is then passed through the line (3a) to the oil / product heat exchanger supply (5) where the pressurized HMFO supply (A') is partially heated by the product HMFO (B). The product HMFO (B) is a stream of hydrocarbons with a sulfur content of less than 5000 ppm in
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36/57 weight and preferably less than 1000 ppm by weight. Hydrocarbons in the feed charge HMFO and product HMFO range between C12 and C O + and the boiling range is between 350 ° F and 1110 + F (176 and 593 + ° C). The pressurized feed load HMFO (A ') passing through the line (5a) is additionally heated against the effluent from the reactor system (E) in the feed of the reactor / effluent heat exchanger (7).
[0063] The heated and pressurized feed charge HMFO (A) in line (7a) is then mixed with activation gas (C) supplied via line (23c) at the mixing point (X) to form a mixture of feed load (D). The mixing point (X) can be any well-known gas / liquid mixing system or entraining system or mechanism well known to the person skilled in the art.
[0064] The feed charge mixture (D) passes through the line (9a) to the reactor feed furnace (9) where the feed charge mixture (D) is heated to the specified process temperature. The reactor feed furnace (9) can be a burning furnace heater or any other type of heater, as known to a person skilled in the art if it raises the temperature of the feed load mixture to the desired temperature for the process conditions .
[0065] The fully heated feed charge mixture (D ') leaves the reactor feed furnace (9) via line 9b and is fed into the reactor system (11). The fully heated feed charge mixture (D ') enters the reactor system (11) where environmental contaminants, such as sulfur, nitrogen, and metals are preferably
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37/57 removed from the feed charge HMFO component of the fully heated feed load mixture. The reactor system contains a catalyst that preferably removes the sulfur compounds in the feed charge HMFO component by reacting them with hydrogen in the activation gas to form hydrogen sulfide. The reactor system will also achieve demetallization, denitrogenation, and a certain amount of ring opening hydrogenation from aromatic complexes and asphaltenes, however minimal hydrocracking of hydrocarbons should occur. The process conditions of partial hydrogen pressure, reaction pressure, temperature and residence time, as measured by time-space velocity, are optimized to obtain the desired final product quality. A more detailed discussion of the reactor system, the catalyst, the process conditions, and other aspects of the process is presented below in the Description of the reactor system.
[0066] The effluent from the reactor system (E) leaves the reactor system (11) via line (11a) and exchanges heat against the pressurized and partially heats the feed charge HMFO (A ') in the reactor / exchanger feed effluent (7). The effluent from the partially cooled reactor system (E ') then flows via line (11c) to the hot separator (13).
[0067] The hot separator (13) separates the gaseous components of the reactor system effluent (F) that are directed to line (13a) from the liquid components of the effluent of the reactor system (G) that are directed to line ( 13b). The gaseous components of the effluent from the in-line reactor system (13a) are cooled against air in the
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38/57 steam-air cooler from the hot separator (15) and then it flows via line (15a) to the cold separator (17).
[0068] The cold separator (17) additionally separates any remaining gaseous components from the liquid components in the cooled gaseous components of the reactor system effluent (F '). The gaseous components of the cold separator (F) are directed to line (17a) and fed over the amine absorber (21). The cold separator (17) also separates any remaining hydrocarbon liquids from the in-line cold separator (H) (17b) from any condensed liquid water from the cold separator (I). The condensed liquid water from the cold separator (I) is sent to OSBL via line (17c) for treatment.
[0069] The hydrocarbon liquid components of the reactor system effluent from the hot separator (G) in line (13b) and hydrocarbon liquid from the cold separator (H) in line (17b) are combined and fed to the extraction system oil product (19). The oil product extractor system (19) removes any residual hydrogen and hydrogen sulfide from the product HMFO (B) that is discharged in line (19b) for storage at the OSBL limits. The ventilation current (M) of the in-line oil product extractor (19a) can be sent to the combustible gas system or the flare-burning system which are within the OSBL limits. A more detailed discussion of the oil product extractor system is presented in the Description of the oil product extractor system Description.
[0070] The gaseous components of the in-line cold separator (F) (17a) contain a mixture of hydrogen, hydrogen sulfide and light hydrocarbons (mainly methane and
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39/57 ethane). This vapor stream (17a) feeds an amine absorber (21) where it is contacted with poor amine (J) supplied at the OSBL limits via line (21a) to the amine absorber (21) to remove hydrogen sulfide from the gases completing the activation gas recycle stream (C '). Rich amine (K) that absorbed hydrogen sulfide leaves the bottom of the amine absorber (21) and is sent OSBL via line (21b) for amine regeneration and sulfur recovery.
[0071] The steam at the top of the inline amine absorber (21c) is preferably recycled to the process as a recycle activation gas (C ') via the recycle compressor (23) and line (23a) where it is mixed with the complementation activation gas (C) supplied OSBL by the line (23b). This mixture of recycle activation gas (C ') and complementation activation gas (C) is to form the activation gas (C) used in the process via line (23c), as noted above. A stream of purified purge gas (H) is drawn from the top vapor line of the amine absorber (21c) and sent via line (21d) to OSBL to prevent the accumulation of light or other non-condensable hydrocarbons.
[0072] Description of reactor system: 0 system of reactor (11) illustrated in Figure 2 comprises a vase in single reactor loaded with the catalyst process and controls, valves and s teachers, as a person versed at
technique would readily appreciate.
[0073] Alternative reactor systems, in which more than
a vase in reactor Can be used in parallel, as shown in Figure 3a or in a cascading series, as shown in Figure 3b, you can r easily replaced fur
single reactor vessel reactor system (11) illustrated in
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40/57
Figure 2. In such an embodiment, each of the multiple reactor vessels is in parallel and similarly charged with a process catalyst and can be supplied with the heated feed mixture (D ') via a common line. The effluent from each of the three reactors is recombined in a common line and forms a combined reactor effluent (E) for further processing, as described above. The illustrative arrangement will allow three reactors to carry out the process in parallel, effectively multiplying the hydraulic capacity of the global reactor system. Control valves and isolation valves can be used to prevent power from entering a reactor vessel, but not another reactor vessel. In this way, a reactor can be diverted and taken out of line for maintenance and refilling of the catalyst while the remaining reactors continue to receive the heated feed charge mixture (D '). It will be appreciated by a person skilled in the art that this arrangement of reactor vessels in parallel is not limited in number to three, but that multiple additional reactor vessels can be added. The only limitation for the number of reactor vessels in parallel is the spacing between batches and the ability to provide heated feed load mix (D ') for each active reactor.
[0074] In another illustrative modality, cascade reactor vessels are loaded with a process catalyst with the same or different activities for metals, sulfur or other environmental contaminants to be removed. For example, a reactor can be charged with a highly active demetallization catalyst, a subsequent second or downstream reactor can be charged with a balanced demetallization / desulfurization catalyst,
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41/57 and a third reactor downstream of the second reactor can be loaded with a highly active desulfurization catalyst. This allows for better control and balance in process conditions (temperature, pressure, spatial flow velocity, etc ...) so that it is suitable for each catalyst. In this way, you can optimize the parameters in each reactor, depending on the material being fed to that specific reactor / catalyst combination and minimize hydrocracking reactions. As with the previous illustrative modality, multiple cascade reactor series can be used in parallel and, thus, the benefits of such an arrangement noted above (ie, allow one series to be online while the other series are offline for maintenance or allow greater capacity of the installation).
[0075] The reactor (s) that form (s) the reactor system can be a fixed bed, boiling bed or mud bed or a combination of these types of reactors. As intended, fixed bed reactors are preferred, as they are easier to operate and maintain.
[0076] The reactor vessel in the reactor system is loaded with one or more process catalysts. The exact design of the process catalyst system is a function of the feed load properties, product requirements and operating limitations, and the optimization of the process catalyst can be accomplished by routine trials and errors by a person skilled in the art.
[0077] The process catalyst (s) comprise at least one metal selected from the group consisting of the metals each belonging to groups 6, 8, 9 and 10 of the Table
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Periodic 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 carrier. The porous inorganic oxide catalyst carrier is at least one carrier selected from the group consisting of alumina, alumina / boron carrier, a metal-containing aluminosilicate carrier, alumina / phosphorus carrier, alumina carrier / alkali metal compound - earthy, alumina / titania carrier and alumina / zirconia carrier. The preferred porous inorganic oxide catalyst carrier is alumina. The pore size and metal loads on the carrier can be systematically varied and tested with the desired feed load and process conditions to optimize the properties of the product HMFO. Such activities are well known and routine for the conversant. The catalyst in the fixed bed reactor (s) can be charged densely or loaded with force.
[0078] The selection of catalyst used within and to charge the reactor system may be preferred to desulfurization when planning a catalyst loading scheme that results in the mixing of the feed charge, first contacting a catalyst bed with a catalyst preferred to demetallization , followed downstream by a catalyst bed with mixed activity for demetallization and desulfurization, followed downstream by a catalyst bed with high desulfurization activity. In effect, the first bed with high demetallization activity acts as a guard bed
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43/57 for the desulfurization bed.
[0079] The purpose of the reactor system is to treat the feed load HMFO to the required stiffness to meet the product HMFO specification. Hydrocarbon demetallization, denitrogenation and hydrogenation reactions can also occur to some extent when the process conditions are optimized, so that the performance of the reactor system reaches the required level of desulfurization. Hydrocracking is preferably minimized to reduce the volume of hydrocarbons formed as hydrocarbon by-products for the process. The objective of the process is to selectively remove environmental contaminants from the feed load HMFO and minimize the formation of unnecessary by-products hydrocarbons (C1-C8 hydrocarbons).
[0080] The process conditions in each reactor vessel will depend on the feed load, the catalyst used and the desired final properties of the desired product HMFO. Variations in conditions can be expected by those skilled in the art and these can be determined by tests in pilot installations and systematic process optimization. With this in mind, it was verified that the operating pressure, the indicated operating temperature, the ratio of the activation gas to feed charge HMFO, the partial pressure of hydrogen in the activation gas and the spatial speed are all parameters important things to consider. The operating pressure of the reactor system should be in the range of 250 psig (1.72 MPa (g)) and 3000 psig (20, 68 MPa (g)), preferably between 1000 psig (6.89 MPa (g)) and 2500 psig (17.23 (MPa (g)) and more preferably between 1500 psig (10.34
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44/57 (MPa (g)) and 2200 psig (15.2 (MPa (g)). The indicated operating temperature of the reactor system should be 500 ° F (260 ° C) to 900 ° F (482 ° C), preferably between 343 ° C (650 ° F) and 850 ° F (454 ° C) and more preferably between 680 ° F (360 ° C) and 800 ° F (426 ° C). activation of the amount of feedstock HMFO should be in the range of 250 scf gas / bbl (7.07921 ^m3 / 158, G 987) of feedstock gas HMFO to 10,000 scf / bbl (m 283.1685 ³ / 158.987 L) HMFO feedstock, preferably between 2,000 scf gas / barrel (56.63369 m ^3/158, G 987) of feedstock gas HMFO to 5000 scf / bbl (141.5842 m ³ / 158.987 L) of feed load HMFO and, more preferably, between 2500 scf gas / barrel (70.79212 m ³ / 158.987 L) of feed load HMFO to 4500 scf gas / barrel (127.4258 m ³ / 158.987 L) feed charge HMFO The activation gas must be selected from mixtures of nitrogen, hydrogen, di carbon oxide, sparkling water, and methane, so the activation gas has an ideal hydrogen gas partial pressure (Ph2) greater than 80% of the total pressure of the activation gas mixture (F) and preferably where the activation has an ideal hydrogen gas partial pressure (ρκ2) greater than 95% of the total pressure of the activation gas mixture (F). The activation gas can have a molar hydrogen fraction in the range between 80% of the total moles of the activation gas mixture and, more preferably, in which the activation gas has a molar hydrogen fraction between 80% and 99% of the moles total of the activation gas mixture. The net hourly space velocity within the reactor system must be between 0.05 oil / hour / m ³ catalyst and 1.0 oil / hour / m ³ catalyst;
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45/57 preferably between 0.08 oil / hour / m ³ catalyst and 0.5 oil / hour / m ³ catalyst and, more preferably, between 0.1 oil / hour / m ³ catalyst and 0.3 oil / hour / m ³ catalyst to achieve desulfurization with sulfur levels in the product below 0.1 wt.
[0081] The hydraulic capacity rate of the reactor system should be between 100 barrels (15898.7 L) of feed load HMFO / day and 100,000 barrels (15898729 L) of feed load HMFO / day, preferably between 1000 barrels (158987 L) of feed load HMFO / day and 60,000 barrels (9539237.7 L) of feed load HMFO / day, more preferably between 5,000 barrels (794936, 5 L) of feed load HMFO / day and 45,000 barrels (7154428.3 L) of feed load HMFO / day, and even more preferably between 10,000 barrels (1589873 L) of feed load HMFO / day and 30,000 barrels (4769618.8 L) of HMFO load feeding / day. The desired hydraulic capacity can be achieved in a single vessel reactor system or in a multiple vessel reactor system.
[0082] Description of oil product extraction system: The oil product extraction system (19) comprises an extraction column and auxiliary equipment and utilities required to remove hydrogen, hydrogen sulfide and lighter light hydrocarbons from HMFO diesel from product. Such systems are well known to a person skilled in the art of which a generalized functional description is presented here. Hot separator liquid (13) and cold separator (7) feed the oil product extraction column (19). Extraction of hydrogen and sulfide from
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46/57 hydrogen and light hydrocarbons lighter than diesel can be obtained via a cooler, live steam, or other means of extraction. The oil product extraction system (19) can be designed with a top system comprising a top condenser, reflux drum and reflux pump, or it can be designed without a top system. The conditions of the oil product extractor can be optimized to control the crude properties of the product HMFO, more specifically viscosity and density.
[0083] Description of the amine absorber system: The amine absorber system (21) comprises the liquid gas contact column and auxiliary equipment and utilities required to remove acid gas (ie hydrogen sulfide) from the steam supply of the cold separator so that the resulting purified gas can be recycled and used as an activation gas. Such systems are well known to a person skilled in the art and a generalized functional description is given here. The vapors from the cold separator (17) feed the contact / system column (19). Poor amine (or other fluids or systems extracting appropriate acid gas) supplied from OSBL is used to purify the vapor from the cold separator so that hydrogen sulfide is effectively removed. The amine absorber system (19) can be designed as a gas drying system to remove any water vapor entrained in the recycle activation gas (C ').
[0084] The following examples will provide a specialist with a more specific illustrative modality to conduct the process described here.
EXAMPLE 1
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47/57 [0085] Overview: The objective of a pilot test cycle is to demonstrate that the feed charge HMFO can be processed through a reactor loaded with commercially available catalysts under specified conditions to remove environmental contaminants, specifically sulfur and others contaminants from the HMFO to produce a product HMFO, which complies with MARPOL, that is, the production of heavy low sulfur marine fuel oil (LS - HMFO) or ultra low sulfur heavy marine fuel oil (USL- HMFO).
[0086] Pilot unit configuration: The pilot unit will be configured with two 434 cm ³ reactors arranged in series to process the feed load HMFO. The first reactor will be loaded with a commercially available hydrodesmetallization catalyst blend (HDM) and a commercially available hydrotransition catalyst (HDT). A person skilled in the art will appreciate that the HDT catalyst layer can be formed and optimized using a mixture of HDM and HDS catalysts combined with an inert material to achieve the desired levels of intermediate / transition activity. The second reactor will be loaded with a commercially available hydrotransition blend (HDT) and a commercially available hydrodesulfurization blend (HDS). Alternatively, the second reactor can be charged simply with a commercially available hydrodesulfurization catalyst (HDS). A person skilled in the art will appreciate that the specific feed properties of the feed load HMFO can affect the proportion of HDM, HDT and HDS catalysts in the
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48/57 reactor system. A systematic process of testing different combinations with the same feed will produce the catalyst combination optimized for any load and reaction load conditions. For this example, the first reactor will be loaded with 2/3 hydrodesmetalization catalyst and 1/3 hydrotransition catalyst. The second reactor will be loaded with all hydrodesulfurization catalysts. The catalysts in each reactor will be mixed with glass beads (approximately 50% by volume) to improve liquid distribution and better control the reactor temperature. For this pilot test cycle, it is possible to use these commercially available catalysts: HDM: Albemarle KFR 20 series or equivalent; HDT: Albemarle KFR 30 series or equivalent; HDS series: Albemarle KFR 50 or KFR 70 or equivalent. Once the pilot unit configuration is complete, the catalyst can be activated by sulphiting the catalyst using dimethyl disulfide (DMDS) in a manner well known to a person skilled in the art.
[0087] Pilot unit operation: Upon completing the activation step, the pilot unit is ready to receive the feed charge and activation gas supply HMFO. For the present example, the activation gas can be of a technical type or better hydrogen gas. The mixed feed charge and activation gas HMFO will be supplied to the pilot plant at rates and operating conditions as specified: oil feed rate: 108.5 ml / h (space speed = 0.25 / h); hydrogen / oil ratio: 570 Nm3 / m3 (3200 scf / barrel); reactor temperature: 372 ° C (702 ° F); reactor outlet pressure: 13.8 MPa (g) (2000 psig).
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49/57 [0088] A person skilled in the art will know which rates and conditions can be systematically adjusted and optimized depending on the feeding properties to achieve the desired product requirements. The unit will be brought to a uniform state for each condition and complete samples taken, so that analytical tests can be completed. The rest of material for each condition will be closed before moving on to the next condition.
[0089] The expected impacts on the feed load HMFO properties are: sulfur content (% by weight): reduced by at least 80%; metal content (% by weight): reduced by at least 80%; MCR / asphaltene content (% by weight): reduced by at least 30%; nitrogen content (% by weight): reduced by at least 20%; Yield Cl-naphtha (wt%): not above 3.0% and preferably not above 1.0%.
[0090] Process conditions at the pilot unit can be systematically adjusted as per Table 4 to assess the impact of process conditions and optimize process performance for the specific feed charge catalyst and HMFO used.
Table 4: Optimization of process conditions Case HC feed rate (ml / h), [LHSV (/ h)] Nm3 H2 / m3 oil / scf H2 / oil barrels Temp(° C / ° F) Pressure (MPa (g) / psig) Baseline 108.5 [0.25] 570/3200 372/702 13.8 / 2000 YOU 108.5 [0.25] 570/3200 362/684 13.8 / 2000 T2 108.5 [0.25] 570/3200 382/720 13.8 / 2000 LI 130.2 [0.30] 570/3200 372/702 13.8 / 2000 L2 86.8 [0.20] 570/3200 372/702 13.8 / 2000 H1 108.5 [0.25] 500/2810 372/702 13.8 / 2000 H2 108.5 [0.25] 640/3590 372/702 13.8 / 2000 SI 65.1 [0.15] 620/3480 385/725 15.2 / 2200
[0091] In this way, the conditions of the pilot unit can
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50/57 can be optimized to reach less than 0.5% by weight of sulfur in the product HMFO and preferably 0.1% by weight of sulfur in the product HMFO. Conditions for producing ULSHMFO (ie 0.1% by weight of sulfur in the product HMFO) will be: feed rate HMFO feed rate: 65.1 ml / h (space speed = 0.15 / h); hydrogen / oil ratio: 620 Nm ³ / m ³ (3480 scf / barrel); reactor temperature: 385 ° C (725 ° F); reactor outlet pressure: 15.2 (MPa (g) (2200 psig))
Table 5 summarizes the anticipated impacts of key HMFO properties.
Table 5 Expected impact of process on key HMFO properties Property Minimum Typical Maximum Sulfur conversion / removal 80% 90% 98% Metal conversion / removal 80% 90% 100% MCR reduction 30% 50% 70% Asphaltene reduction 30% 50% 70% Nitrogen conversion 10% 30% 70% Yield Cl to naphtha 0.5% 1.0% 4.0% Hydrogen consumption (scf / barrel) 500 750 1500
[0092] Table 6 lists analytical tests to be carried out to characterize the feed load HMFO and product HMFO. Analytical tests include those required by ISO for feed load HMFO and product HMFO to qualify and market as ISO compliant marine waste oils. Additional parameters are provided, so that a person skilled in the art will be able to understand and specify the effectiveness of the inventive process
Table 6 Analytical tests and test procedures Sulphur content ISO 8754 or ISO 14596 orASTM D4294 Density @ 15 ° C ISO 3675 or ISO 12185 Kinematic viscosity @ 50 ° C ISO 3104
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Drop point, ° C ISO 3016 Flash point, ° C ISO 2719 CCAI ISO 8217, ANNEX B Ash content ISO 6245 Total sediment - aged ISO 10307-2 Micro-carbon residue, mass% ISO 10370 H2S, mg / kg IP 570 acid index ASTM D664 Water ISO 3733 Specific contaminants IP 501 or IP 470 (unless otherwise stated) Vanadium or ISO 14597 SodiumAluminum or ISO 10478 Silicon or ISO 10478 Calcium or IP 500 Zinc or IP 500 Phosphor IP 500 NickelIronDistillation ASTM D7169 Ratio C: H ASTM D3178 SARA Analysis ASTM D2007 Asphaltenes,% by weight ASTM D6560 Total nitrogen ASTM D5762 Ventilation gas component analysis FID or comparable gas chromatography
[0093] Table 7 contains the results of the feed load HMFO analytical test and the product HMFO analytical test results expected from the inventive process, which indicate the production of an LS HMFO. It will be noted by a person skilled in the art that, under the conditions, hydrocarbon cracking levels will be minimized to levels substantially less than 10%, more preferably less than 5% and even more preferably less than 1% of the rest of the total mass .
Table 7 Analytical resultsFeed load HMFO Product HMFO sulfur content,% by weight 3.0 0.3
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Density @ 15 C, kg / m ³ 990 950 ⁽¹⁾ Kinematic viscosity @ 50C, mm ² / s 380 100 ⁽¹⁾ Drop point, C 20 10 Flash point, C 110 100 ⁽¹⁾ CCAI 850 820 Ash content,% by mass 0.1 0.0 Total aged sediment,% by mass 0.1 0.0 Micro-carbon residue, mass% 13.0 6.5 H2S, mg / kg 0 0 acid number, mg KO / g 1 0.5 Water,% by volume 0.5 0 Specific contaminants, mg / kg Vanadium 180 20 Sodium 30 1 Aluminum 10 1 Silicon 30 3 Calcium 15 1 Zinc 7 1 Phosphor 2 0 Nickel 40 5 Iron 20 2 Distillation, ° C / ° F IBP 160/320 120/248 5% by weight 235/455 225/437 10% by weight 290/554 270/518 30% by weight 410/770 370/698 50% by weight 540/1004 470/878 70% by weight 650/1202 580/1076 90% by weight 735/1355 660/1220 FBP 820/1508 730/1346 Ratio C: H (ASTM D3178) 1.2 1.3 SARA Analysis Saturated 16 22 Aromatic 50 50 Resins 28 25 Asphaltenes 6 3 Asphaltenes,% by weight 6, 0 2.5 Total nitrogen, mg / kg 4000 3000 Note: (1) It is expected that the property will be adjusted to a higher value by the post-process removal of light material via distillation or extraction of the product HMFO.
[0094] The product HMFO produced by the process
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The inventive 53/57 will achieve ULS limits for HMFO (ie 0.1% by weight of sulfur in the product HMFO) by systematic variation of process parameters, for example, by a lower spatial speed or using a load HMFO with a lower initial sulfur content.
EXAMPLE 2: RMG-380 HMFO [0095] Pilot unit configuration: A pilot unit will be configured as noted above in Example 1 with the following changes: the first reactor was loaded with: as the first (top) layer found by the supply load , 70% by volume of Albemarle KFR 20 series hydrodesmetallisation catalyst and 30% by volume of Albemarle KFR 30 series hydro transition catalyst as the second (bottom) layer. The second reactor was loaded with 20% Albemarle KFR 30 series hydro-transition catalyst as the first layer (top) and 80% hydrodesulfurization catalyst as the second layer (bottom). The catalyst was activated by sulfating the catalyst with dimethyl disulfide (DMDS) in a manner well known to those skilled in the art.
[0096] Pilot unit operation: Upon completing the activation step, the pilot unit was ready to receive the feed load HMFO and activation gas. The activation gas was of a technical type or better hydrogen gas. The feed load HMFO was a commercially available and salable HMFO in accordance with ISO 8217: 2017, except for the high sulfur content (2.9% by weight). The mixed feed charge and activation gas HMFO were supplied to the pilot plant at rates and conditions as specified in Table 8 below. The conditions
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54/57 were varied to optimize the level of sulfur in the product HMFO material.
Table 8: Process conditions Product HMFO Case HC feed rate (ml / h), [LHSV (/ h)] Nm ³ H2 / m ³ oil / scf H2 / oil barrel Temp(° C / ° F) Pressure (MPa (g) / psig) Sulfur% by weight Baseline 108.5 [0.25] 570/3200 371/700 13.8 / 2000 0, 24 YOU 108.5 [0.25] 570/3200 362/684 13.8 / 2000 0.53 T2 108.5 [0.25] 570/3200 382/720 13.8 / 2000 0.15 LI 130.2 [0.30] 570/3200 372/702 13.8 / 2000 0.53 SI 65.1 [0.15] 620/3480 385/725 15.2 / 2200 0.10 PI 108.5 [0.25] 570/3200 371/700 / 1700 0.56 T2 / P1 108.5 [0.25] 570/3200 382/720 / 1700 0.46
[0097] Analytical data for a representative sample of feed load HMFO and representative samples of product HMFO are shown below:
Table 7 Analytical results - HMFO (RMG — 380)Feed load Product Product Sulfur content,% by mass 2, 9 0.3 0.1 Density @ 15 ° C, kg / m ³ 988 932 927 Kinematic viscosity @ 50 ° C, mm ² / s 382 74 47 Drop point, ° C -3 -12 -30 Flash point, ° C 116 96 90 CCAI 850 812 814 Ash content,% by mass 0.05 0, 0 0, 0 Total aged sediment,% by mass 0.04 0, 0 0, 0 Microcarbon residue,% by mass 11, 5 3, 3 4, 1 H2S, mg / kg 0, 6 0 0 acid number, mg KO / g 0, 3 0, 1 > 0.05 Water,% by volume 0 0, 0 0, 0 Specific contaminants, mg / kg Vanadium 138 15 <1 Sodium 25 5 2
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Aluminum 21 2 <1 Silicon 16 3 1 Calcium 6 2 <1 Zinc 5 <1 <1 Phosphor <1 2 1 Nickel 33 23 2 Iron 24 8 1 Distillation, ° C / ° F IBP 178/352 168/334 161/322 5% by weight 258/496 235/455 230/446 10% by weight 298/569 270/518 264/507 30% by weight 395/743 360/680 351/664 50% by weight 517/962 461/862 439/822 70% by weight 633/1172 572/1062 552/1026 90% by weight > 720 /> 1328 694/1281 679/1254 FBP > 720 /> 1328 > 720 /> 1328 > 720 /> 1328 Ratio C: H (ASTM D3178) 1, 2 1, 3 1, 3 SARA Analysis Saturated 25, 2 28, 4 29, 4 Aromatic 50, 2 61, 0 62.7 Resins 18, 6 6, 0 5, 8 Asphaltenes 6, 0 4, 6 2, 1 Asphaltenes,% by weight 6, 0 4, 6 2, 1 Total nitrogen, mg / kg 3300 1700 1600
[0098] As noted above in Table 7, both the feed charge HMFO and the product HMFO observed the properties consistent with ISO 8217: 2017 for a marketable residual marine fuel oil, except that the sulfur content of the product HMFO was significantly reduced, as noted above, when compared to the feed load HMFO.
[0099] A person skilled in the art will appreciate that the
Product HMFO above, produced by the inventive process, not only achieved an HMFO LS in accordance with ISO 8217: 2017 (ie 0.5% by weight of sulfur), but also a product HMFO within the limits of ULS HMFO in in accordance with ISO 8217: 2017 ULS (ie 0.1% by weight of sulfur).
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EXAMPLE 3: RMK-500 HMFO [00100] The supply load for the pilot reactor used in example 2 above was changed to a commercially available and salable HMFO in accordance with ISO 8217: 2017 RMK-500, except that it had a high content environmental contaminants (ie sulfur (3.3% by weight)). Other raw characteristics of the RMK-500 high sulfur feed load HMFO are shown below:
Table 8 Analytical results - feed load HMFO (RMK-500) Sulfur content,% by mass 3, 3 Density @ 15 ° C, kg / m ³ 1006 Kinematic viscosity @ 50 ° C, mm ² / s 500
[00101] The feed charge HMFO (RMK-500) and the mixed activation gas were supplied to the pilot plant and the resulting sulfur conditions and levels obtained are shown in the table below.
Table 9: Process conditions Product (RMK500) Case HC feed rate (ml / h), [LHSV (/ h)] Nm ³ H / m ³ oil / scf H ₂ / oil barrels Temp(° C / ° F) Pressure (MPa (g) / psig) % insulfur weight THE 108.5 [0.25] 640/3600 377/710 13.8 / 2000 0.57 B 95.5 [0.22] 640/3600 390/735 13.8 / 2000 0.41 Ç 95.5 [0.22] 640/3600 390/735 11.7 / 1700 0.44 D 95.5 [0.22] 640/3600 393/740 10.3 / 1500 0.61 AND 95.5 [0.22] 640/3600 393/740 17.2 / 2500 0.37 F 95.5 [0.22] 640/3600 393/740 8.3 / 1200 0.70 G 95.5 [0.22] 640/3600 416/780 8.3 / 1200 0.37
[00102] The resulting product (RMK-500) HMFO exhibited observed crude properties consistent with the feed load HMFO (RMK-500), except that the sulfur content was significantly reduced, as noted in the table above.
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57/57 [00103] A person skilled in the art will appreciate that the above product HMFO, produced by the inventive process, has achieved a product HMFO of type HMFO LS (ie 0.5% by weight of sulfur) having characteristics in crude from a residual fuel oil RMK-500 in accordance with ISO 8217: 2017. It will also be appreciated that the process can be carried out successfully under non-hydrocracking conditions (ie lower temperature and pressure) that substantially reduce hydrocracking of the power load. It should be noted that when conditions were increased to a much higher pressure (Example E), a product with a lower sulfur content was achieved, however it was observed that there was an increase in the production of light hydrocarbons and wild naphtha.
[00104] It will be appreciated by those versed in the technique that changes can be made in the described illustrative modalities, without leaving their broad inventive concepts. Thus, it should be understood that the inventive concepts described are not limited to the illustrative modalities or examples described, but if desired that they cover changes in the scope of the inventive concepts, as defined in the claims.

权利要求:
Claims (18)
[1]
1. Low sulfur heavy marine fuel oil, characterized by the fact that it essentially consists of a 100% hydroprocessed high sulfur heavy marine fuel oil, in which, prior to hydroprocessing, the high sulfur heavy marine fuel oil is according to ISO 8217: 2017 and is of marketable quality as a residual marine fuel oil, but has a sulfur content (ISO 14596 or ISO 8754) greater than 0.5% by weight, and in which heavy marine fuel oil low sulfur content complies with ISO 8217: 2017 and is of marketable quality as a residual marine fuel oil and has a sulfur content (ISO 14596 or ISO 8754) of less than 0.5% by weight.
[2]
2. Composition according to claim 1, characterized by the fact that heavy marine fuel oil with a high sulfur content has a sulfur content (ISO 14596 or ISO 8754) in the range of 1.0% by weight at 5, 0% by weight, and low sulfur heavy marine fuel oil has a sulfur content (ISO 14596 or ISO 8754) in the range of 0.5% by weight and 0.05% by weight.
[3]
3. Composition according to claim 1, characterized by the fact that heavy marine fuel oil with a low sulfur content has a sulfur content (ISO 14596 or ISO 8754) less than 0.1% by weight.
[4]
4. Composition according to claim 1, characterized by the fact that heavy low-sulfur marine fuel oil has a maximum kinematic viscosity at 50C (ISO 3104) between the range of 180 mm ² / s to 700 mm ² / s; maximum density at 15 ° C (ISO 3675) between the
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2/8 range from 991.0 kg / m ³ to 1010.0 kg / m ³ ; CCAI is in the range of 780 to 870; a flash point (ISO 2719) of not less than 60.0 ° C and a maximum total - aged sediment (ISO 10307-2) of 0.10% by weight; a maximum carbon residue - micro method (ISO 10370) between the range of 18.00% by weight and 20.00% by weight, and a maximum content of aluminum plus silicon (ISO 10478) of 60 mg / kg.
[5]
5. Low sulfur hydrocarbon fuel composition characterized by the fact that it consists essentially of: a majority by volume of a 100% hydroprocessed high-sulfur residual marine fuel oil and a minority by volume of diluent materials, in which before hydroprocessing, heavy marine sulfur fuel oil complies with ISO 8217: 2017, but has a sulfur content (ISO 14596 or ISO 8754) greater than 0.5% by weight; and where the composition of low sulfur heavy marine fuel is in accordance with ISO 8217: 2017 and has a sulfur content (ISO 14596 or ISO 8754) of less than 0.5% by weight; and in which diluting materials are selected from the group consisting of: hydrocarbon materials; non-hydrocarbon materials; and, solid materials and combinations thereof.
[6]
6. Composition according to claim 5, characterized by the fact that the residual marine fuel oil with high sulfur content 100% hydroprocessed totals at least 75% in volume of the composition and the diluent materials are not more than 25% in volume of the composition.
[7]
7. Composition according to claim 5,
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3/8 characterized by the fact that the residual marine fuel oil with high sulfur content 100% hydroprocessed totals at least 90% in volume of the composition and the diluent materials are not more than 10% in volume of the composition.
[8]
8. Composition according to claim 5, characterized by the fact that hydrocarbon materials are selected from the group consisting of: heavy marine fuel oil with a sulfur content (ISO 14596 or ISO 8754) greater than 0.5 in Weight; distillate-based fuels; diesel; diesel; marine diesel; marine diesel oil; cutting oil; biodiesel; methanol, ethanol; synthetic hydrocarbons and oils based on gas technology for liquids; Fischer-Tropsch-derived oils; synthetic oils based on polyethylene, polypropylene, dimer, trimer and poly butylene; atmospheric residue; vacuum residue; fluidized catalytic cracker slurry oil (FCC); FCC cycle oil; pyrolysis gas oil; cracked light diesel (CLGO); cracked heavy diesel (CHGO); light cycle oil (LCO); heavy cycle oil (HCO); thermally cracked residue; heavy coke distillate; bitumen; heavy asphalted oil; viscorreduction residue; tailing oils; asphalt oils; used or recycled engine oils; aromatic extracts of lubricating oil; crude oil; heavy crude oil; 'unfavorable' crude oil; and combination thereof; and in which non-hydrocarbon materials are selected from the group consisting of: residual water; detergents; viscosity modifiers; gout point depressants; lubricity modifiers; mist removers; antifoaming agents;
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4/8 ignition enhancers; antirust agents; corrosion inhibitors; anti-wear additives, antioxidants (for example, phenolic compounds and derivatives), coating agents and surface modifiers, metal deactivators, static dissipating agents, ionic and non-ionic surfactants, stabilizers, colorants and cosmetic odorants and combinations thereof; and, in which the solid materials are selected from the group consisting of: hydrocarbon or carbon solids; coke; graphitic solids; micro-agglomerated asphaltenes, iron rust; oxidative corrosion solids; raw metal particles; paint particles; surface coating particles; plastic particles or polymeric particles or elastomer particles and rubber particles; fine catalysts; ceramic particles; mineral particles; sand; clay; clay particles; bacteria; biologically generated solids; and combination of them
[9]
9. Composition according to claim 4, characterized by the fact that heavy marine fuel oil with low sulfur content has a maximum kinematic viscosity at 50C (ISO 3104) between the range of 180 mm ^{* 2} / s to 700 mm ² /s; a maximum density at 15 ° C (ISO 3675) between the range of 991.0 kg / m ³ to 1010.0 kg / m ³ ; a CCAI is in the range of 780 to 870; a flash point (ISO 2719) of not less than 60.0 ° C and a maximum total - aged sediment (ISO 103072) of 0.10% by weight; a maximum carbon residue - micro method (ISO 10370) between the range of 18.00% by weight and 20.00% by weight, and a maximum content of aluminum plus silicon (ISO 10478) of 60 mg / kg.
[10]
10. Composition of marine fuel oil
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5/8 heavy characterized by the fact that it comprises: at least 50% by volume of a hydroprocessed residual marine fuel oil and no more than 50% by volume of diluent materials selected from the group consisting of: hydrocarbon materials; non-hydrocarbon materials; and solid materials and combinations thereof.
[11]
11. Composition according to claim 10, characterized by the fact that before hydroprocessing, hydroprocessed residual marine fuel oil has a sulfur content (ISO 14596 or ISO 8754) between the range of 5.0% by weight at 1 , 0% by weight and has: a maximum kinematic viscosity at 50C (ISO 3104) between the range of 180 mm ² / s to 700 mm ² / s and a maximum density at 15 ° C (ISO 3675) between the range of 991.0 kg / m ³ to 1010.0 kg / m ³ and a CCAI is in the range of 780 to 870 and a flash point (ISO 2719) of not less than 60.0 ° C and a maximum total aged sediment (ISO 10307-2 ) of 0.10% by weight and a maximum carbon residue - micro method (ISO 10370) between the range of 18.00% by weight and 20.00% by weight and a maximum vanadium content (ISO 14597) between 350 mg / kg to 450 ppm mg / kg and a maximum aluminum plus silicon content (ISO 10478) of 60 mg / kg.
[12]
12. Composition, according to claim 10, characterized by the fact that the hydroprocessed residual marine fuel oil has a sulfur content (ISO 14596 or ISO 8754) between the range of 0.5% by weight and 0.05% in weight and has: a maximum kinematic viscosity at 50C (ISO 3104) between the range of 180 mm ² / s to 700 mm ² / s and a maximum density at 15 ° C (ISO 3675) between the range of 991.0 kg / m ³ at 1010.0 kg / m ³ and a CCAI is in the range of 780 to 870 and a flash point (ISO 2719) of not less than 60.0 ° C and a sediment
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6/8 maximum total - aged (ISO 10307-2) 0.10% by weight and a maximum carbon residue - micro method (ISO 10370) between the range of 18.00% by weight and 20.00% by weight and a maximum vanadium content (ISO 14597) between the range of 350 mg / kg to 450 ppm mg / kg and a maximum aluminum plus silicon content (ISO 10478) of 60 mg / kg.
[13]
13. Composition according to claim 11, characterized by the fact that hydrocarbon materials are selected from the group consisting of: heavy marine fuel oil with a sulfur content (ISO 14596 or ISO 8754) greater than 0.5 weight ; distillate-based fuels; diesel; diesel; marine diesel; marine diesel oil; cutting oil; biodiesel; methanol, ethanol; synthetic hydrocarbons and oils based on gas technology for liquids; oils derived from FischerTropsch; synthetic oils based on polyethylene, polypropylene, dimer, trimer and poly butylene; atmospheric residue; vacuum residue; fluidized catalytic cracker slurry oil (FCC); FCC cycle oil; pyrolysis gas oil; cracked light diesel (CLGO); cracked heavy diesel (CHGO); light cycle oil (LCO); heavy cycle oil (HCO); thermally cracked residue; heavy coke distillate; bitumen; heavy asphalted oil; viscorreduction residue; tailing oils; asphalt oils; used or recycled engine oils; aromatic extracts of lubricating oil; crude oil; heavy crude oil; 'unfavorable' crude oil; and combination thereof; and in which non-hydrocarbon materials are selected from the group consisting of: residual water; detergents; viscosity modifiers; depressants of
Petition 870190077705, of 12/08/2019, p. 31/34
7/8 drop point; lubricity modifiers; mist removers; antifoaming agents; ignition enhancers; antirust agents; corrosion inhibitors; anti-wear additives, antioxidants (for example, phenolic compounds and derivatives), coating agents and surface modifiers, metal deactivators, static dissipating agents, ionic and non-ionic surfactants, stabilizers, colorants and cosmetic odorants and combinations thereof; and in which the solid materials are selected from the group consisting of: hydrocarbon or carbon solids; coke; graphical solids; micro-agglomerated asphaltenes, iron rust; oxidative corrosion solids; raw metal particles; ink particles; surface coating particles; plastic particles or polymeric particles or elastomer particles and rubber particles; fine catalysts; ceramic particles; mineral particles; sand; clay; clay particles; bacteria; biologically generated solids; and combination of them
[14]
14. Composition, according to claim 10, characterized by the fact that the volume of hydroprocessed residual marine fuel oil totals at least 75% by volume of the composition and the diluent materials are not more than 25% by volume of the composition.
[15]
15. Composition according to claim 10, characterized by the fact that the volume of hydroprocessed residual marine fuel oil totals at least 90% by volume of the composition and the diluent materials are not more than 10% by volume of the composition.
[16]
16. Composition, according to claim
Petition 870190077705, of 12/08/2019, p. 32/34
8/8
10, characterized by the fact that the volume of the hydroprocessed residual marine fuel oil totals at least 95% in volume of the composition and the diluent materials are not more than 5% in volume of the composition.
[17]
17. Composition according to claim 10, characterized by the fact that the heavy marine fuel oil composition is in accordance with ISO 8217: 2017 and has a sulfur content (ISO 14596 or ISO 8754) between the range of 0, 5% by weight and 0.05% by weight.
[18]
18. Composition, according to claim 17, characterized by the fact that the composition of heavy marine fuel oil is of marketable quality.

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法律状态:
2021-10-19| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201762458002P| true| 2017-02-12|2017-02-12|

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US201762589479P| true| 2017-11-21|2017-11-21|

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PCT/US2018/017863|WO2018148681A1|2017-02-12|2018-02-12|Heavy marine fuel oil composition|

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