PROCESS AND DEVICE FOR REDUCING ENVIRONMENTAL CONTAMINATES IN HEAVY MARINE FUEL OIL

Abstract

A process for reducing the environmental contaminants in a ISO 8217 compliant Feedstock Heavy Marine Fuel Oil, the process involving: mixing a quantity of the Feedstock Heavy Marine Fuel Oil with a quantity of Activating Gas mixture to give a feedstock mixture; contacting the feedstock mixture with one or more catalysts to form a Process Mixture from the feedstock mixture; separating the Product Heavy Marine Fuel Oil liquid components of the Process Mixture from the gaseous components and by-product hydrocarbon components of the Process Mixture and, discharging the Product Heavy Marine Fuel Oil. The Product Heavy Marine Fuel Oil is compliant with ISO 8217 for residual marine fuel oils and has a sulfur level has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 % wt. to 0.5 % wt.. The Product Heavy Marine Fuel Oil can be used as or as a blending stock for an ISO 8217 compliant, IMO MARPOL Annex VI (revised) compliant low sulfur or ultralow sulfur heavy marine fuel oil. A device for conducting the process is also disclosed.

Claims

1. A process for reducing Environmental Contaminants in a Feedstock Heavy Marine Fuel Oil, the process comprising: mixing a quantity of Feedstock Heavy Marine Fuel Oil, wherein the Feedstock Heavy Marine Fuel Oil is compliant with ISO 8217:2017 as a Table 2 residual marine fuel oil, except the Environmental Contaminants content is greater than 0.5 %wt and wherein the Environmental Contaminants are selected from the group consisting of sulfur, vanadium, nickel, iron, aluminum and silicon and combinations thereof, with a quantity of Activating Gas mixture to give a feedstock mixture; contacting the feedstock mixture with one or more catalysts under reactive conditions to form a Process Mixture from said feedstock mixture, wherein the Process Mixture contains one or more Product Heavy Marine Fuel Oil liquid components, wherein the reactive conditions are selected to achieve a level of hydrocracking of the Feedstock Heavy Marine Fuel Oil of less than 10% of the total mass balance; separating the one or more Product Heavy Marine Fuel Oil liquid components of the Process Mixture from the Process Mixture to form a Product Heavy Marine Fuel Oil; and discharging the Product Heavy Marine Fuel Oil.

2. The process of claim 1, wherein said Feedstock Heavy Marine Fuel Oil has a sulfur content as determined by ISO 14596 or ISO 8754 between the range of 5.0 %wt to 1.0 %wt.

3. The process of claim 1, wherein said Product Heavy Marine Fuel Oil has bulk properties that comply with ISO 8217:2017 as a Table 2 residual marine fuel oil and has a maximum sulfur content as determined by ISO 14596 or ISO 8754 between the range of 0.05 %wt to 0.50 %wt.

4. The process of claim 1, wherein the contacting of the feedstock mixture with one or more catalysts under reactive conditions are selected to hydrodemetallize the Feedstock Heavy Marine Fuel Oil to a level of metals removal greater than 80% of the metal content of the Feedstock Heavy Marine Fuel Oil and are selected to hydrodesulfurize the Feedstock Heavy Marine Fuel Oil to a level of sulfur removal greater than 80% of the sulfur content of the Feedstock Heavy Marine Fuel Oil and are selected to have a hydrogen consumption in the range between 500 and 1500 scf/bbl of Feedstock Heavy Marine Fuel Oil.

5. The process of claim 1, wherein said Activating Gas mixture is selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseous water, and methane, such that the Activating Gas mixture has an ideal gas partial pressure of hydrogen (p.sub.H2) greater than 80% of a total pressure of the Activating Gas mixture (P), and wherein the reactive conditions include a ratio of the quantity of the Activating Gas mixture to the quantity of Feedstock Heavy Marine Fuel Oil in the range of 250 scf gas / bbl of Feedstock Heavy Marine Fuel Oil to 10,000 scf gas / bbl of Feedstock Heavy Marine Fuel Oil, a total pressure between of 250 psig and 3000 psig, and an indicated temperature between of 500° F. to 900° F., and, a liquid hourly space velocity between 0.05 /hour and 1.0 /hour.

6. A process for reducing the environmental contaminants in a Feedstock Heavy Marine Fuel Oil, the process comprising: mixing a quantity of Feedstock Heavy Marine Fuel Oil, wherein the Feedstock Heavy Marine Fuel Oil is compliant with ISO 8217:2017 as a Table 2 residual marine fuel oil, except the sulfur content as determined by ISO 14596 or ISO 8754 is greater than 0.5 %wt, with a quantity of Activating Gas, wherein the Activating Gas has an ideal gas partial pressure of hydrogen (p.sub.H2) greater than 80% of a total pressure of the Activating Gas (P) to give a feedstock mixture; providing the feedstock mixture to at least one reactor vessel and contacting the feedstock mixture under reactive conditions in said at least one reactor vessel with one or more hydrotreating catalysts to form a Process Mixture from said feedstock mixture wherein said Process Mixture includes a liquid Product Heavy Marine Fuel Oil component, wherein the reactive conditions are selected to achieve a level of hydrocracking of the Feedstock Heavy Marine Fuel Oil of less than 10% of the total mass balance; receiving said Process Mixture in at least one separating vessel and separating the liquid Product Heavy Marine Fuel Oil components of the Process Mixture from the Process Mixture; discharging the Product Heavy Marine Fuel Oil components from the at least one separating vessel.

7. The process of claim 6, wherein said Feedstock Heavy Marine Fuel Oil has a sulfur content as determined by ISO 14596 or ISO 8754 between the range of 5.0 %wt to 1.0 %wt.

8. The process of claim 7, wherein said Product Heavy Marine Fuel Oil components have a sulfur content as determined by ISO 14596 or ISO 8754 less than 0.5 %wt, a kinematic viscosity at 50° C. as determined by ISO 3104 and a density at 15° C. as determined by ISO 3675 to give a CCAI in the range of 780 to 870, a flash point as determined by ISO 2719 no lower than 60.0° C., and a maximum total sediment - aged as determined by ISO 10307-2 of 0.10 %wt.

9. The process of claim 7, wherein the receiving said Process Mixture in at least two separating vessels and separating the liquid Product Heavy Marine Fuel Oil components of the Process Mixture from the Process Mixture.

10. The process of claim 7 wherein the reactive conditions include a ratio of the quantity of the Activating Gas to the quantity of Feedstock Heavy Marine Fuel Oil in the range of 250 scf gas / bbl of Feedstock Heavy Marine Fuel Oil to 10,000 scf gas / bbl of Feedstock Heavy Marine Fuel Oil, a total pressure between 250 psig and 3000 psig, an indicated temperature between 500° F. to 900° F., and a liquid hourly space velocity within the at least one reactor vessel is between 0.05 /hour and 1.0 /hour.

11. The process of claim 6, wherein the contacting of the Feedstock Mixture with one or more metal heterogeneous catalysts under reactive conditions are selected to hydrodemetallize the Feedstock Heavy Marine Fuel Oil to a level of metals removal greater than 80% of the metal content of the Feedstock Heavy Marine Fuel Oil and are selected to hydrodesulfurize the Feedstock Heavy Marine Fuel Oil to a level of sulfur removal greater than 80% of the sulfur content of the Feedstock Heavy Marine Fuel Oil and are selected to have a hydrogen consumption in the range between 500 and 1500 scf/bbl of Feedstock Heavy Marine Fuel Oil.

12. The process of claim 11, wherein said at least one reactor vessel contains one or more transition metal heterogeneous catalysts and is configured to include at least two reactor vessels, wherein each reactor independently selected from the group consisting of: an ebulliated bed reactor, a fixed bed reactor, and combinations thereof.

13. The process of claim 11, wherein the one or more transition metal heterogeneous catalyst comprises: a porous inorganic oxide catalyst carrier and impregnated with a blend of transition metal catalyst materials, wherein the porous inorganic oxide catalyst carrier is alumina and wherein the transition metal catalyst materials are selected from the group consisting of Ni—Mo, Co—Mo, Ni—W or Ni — Co—Mo.

14. The process of claim 6, wherein said Product Heavy Marine Fuel Oil is compliant with ISO 8217:2017 as a Table 2 residual marine fuel oil and has a maximum sulfur content as determined by ISO15596 or ISO8754 between the range of 0.05 %wt to 0.5 %wt.

15. The process of claim 6, wherein said Product Heavy Marine Fuel Oil has: has a maximum sulfur content as determined by ISO15596 or ISO8754 between the range of 0.05 %wt to 0.5 %wt, a kinematic viscosity at 50° C. as determined by ISO 3104 and a density at 15° C. as determined by ISO 3675 to give a CCAI is in the range of 780 to 870 and a flash point as determined by ISO 2719 no lower than 60.0° C., and a maximum total sediment - aged as determined by ISO 10307-2 of 0.10 % wt.

16. A device for reducing environmental contaminants in a Feedstock Heavy Marine Fuel Oil, the device comprising: at least one first vessel for receiving a quantity of the Feedstock Heavy Marine Fuel Oil mixed with a quantity of an Activating Gas and contacting the mixture with one or more catalysts to form a Process Mixture; at least one second vessel in fluid communication with the first vessel, said second vessel for receiving said Process Mixture from said first vessel, wherein said second vessel separates the liquid components of the Process Mixture from the Process Mixture; and means for discharging a Product Heavy Marine Fuel Oil.

17. The device of claim 16, wherein the at least one first vessel is comprised of two or more reactor vessels, wherein each of the two or more reactor vessels is independently selected from the group consisting of an ebulliated bed reactor, a fixed bed reactor, and combinations thereof and wherein each of the two or more reactor vessels contains one or more transition metal heterogeneous catalysts under reactive conditions that are selected from the group of reactive conditions consisting of hydrodemetallization the Feedstock Heavy Marine Fuel Oil to a level of metals removal greater than 80% of the metal content of the Feedstock Heavy Marine Fuel Oil, hydrodesulfurization the Feedstock Heavy Marine Fuel Oil to a level of sulfur removal greater than 80% of the sulfur content of the Feedstock Heavy Marine Fuel Oil, and combinations thereof; and wherein the reactive conditions are selected to have a hydrogen consumption in the range between 500 and 1500 scf/bbl of Feedstock Heavy Marine Fuel Oil.

18. The device of claim 17, wherein the one or more transition metal heterogeneous catalysts comprises: a porous inorganic oxide catalyst carrier and a transition metal catalyst, wherein the preferred porous inorganic oxide catalyst carrier is alumina and wherein the preferred transition metal catalyst is Ni—Mo, Co—Mo, Ni—W or Ni — Co—Mo.

19. The device of claim 16, wherein said Feedstock Heavy Marine Fuel Oil has bulk properties that comply with ISO 8217:2017 as a Table 2 residual marine fuel and has a sulfur content (ISO 14596 or ISO 8754) between the range of 5.0 %wt to 1.0 %wt.

20. The device of claim 16, wherein the maximum sulfur content (ISO 14596 or ISO 8754) of said Product Heavy Marine Fuel Oil is between 1% and 10% of the maximum sulfur content of the Feedstock Heavy Marine Fuel Oil.

Description

DESCRIPTION OF DRAWINGS

[0027] 027. FIG. 1 is a process flow diagram of a process to produce Product HMFO.

[0028] 028. FIG. 2 is a basic schematic diagram of a plant to produce Product HMFO.

[0029] 029. FIG. 3a is a basic schematic diagram of a first alternative variation of the Reactor Section in a plant to produce Product HMFO in the second illustrative embodiment.

[0030] 030. FIG. 3b is a basic schematic diagram of a second alternative variation of the Reactor Section in a plant to produce Product HMFO in the second illustrative embodiment.

DETAILED DESCRIPTION

[0031] 031. The inventive concepts as described herein utilize terms that should be well known to one of skill in the art, however certain terms are utilized having a specific intended meaning and these terms are defined below: [0032] Heavy Marine Fuel Oil (HMFO) is a petroleum product fuel compliant with the ISO 8217 :2017 standards for the bulk properties of residual marine fuels except for the concentration levels of the Environmental Contaminates. [0033] Environmental Contaminates are organic and inorganic components of HMFO that result in the formation of SO.sub.x, NO.sub.x and particulate materials upon combustion. [0034] Feedstock HMFO is a petroleum product fuel compliant with the ISO 8217 :2017 standards for the bulk properties of residual marine fuels except for the concentration of Environmental Contaminates, preferably the Feedstock HMFO has a sulfur content greater than the global MARPOL standard of 0.5% wt. sulfur, and preferably and has a sulfur content (ISO 14596 or ISO 8754) between the range of 5.0 % wt. to 1.0 % wt. sulfur (ISO 14596 or ISO 8754). [0035] Product HMFO is a petroleum product fuel compliant with the ISO 8217 :2017 standards for the bulk properties of residual marine fuels and achieves a sulfur content lower than the global MARPOL standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754), and preferably a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 % wt. to 1.0 % wt. [0036] Activating Gas: is a mixture of gases utilized in the process combined with the catalyst to remove the environmental contaminates from the Feedstock HMFO. [0037] Fluid communication: is the capability to transfer fluids (either liquid, gas or combinations thereof, which might have suspended solids) from a first vessel or location to a second vessel or location, this may encompass connections made by pipes (also called a line), spools, valves, intermediate holding tanks or surge tanks (also called a drum). [0038] Merchantable quality: is a level of quality for a residual marine fuel oil so that the fuel is fit for the ordinary purpose it is intended to serve (i.e. serve as a residual fuel source for a marine ship) and can be commercially sold as and is fungible with heavy or residual marine bunker fuel. [0039] Bbl or bbl: is a standard volumetric measure for oil; 1 bbl = 0.1589873 m.sup.3; or 1 bbl = 158.9873 liters; or 1 bbl = 42.00 US liquid gallons. [0040] Bpd: is an abbreviation for Bbl per day. [0041] SCF: is an abbreviation for standard cubic foot of a gas; a standard cubic foot (at 14.73 psi and 60° F. ) equals 0.0283058557 standard cubic meters (at 101.325 kPa and 15° C. ).

[0042] 032. The inventive concepts are illustrated in more detail in this description referring to the drawings, in which FIG. 1 shows the generalized block process flows for reducing the environmental contaminates in a Feedstock HMFO and producing a Product HMFO according to a first illustrative embodiment. A predetermined volume of Feedstock HMFO (2) is mixed with a predetermined quantity of Activating Gas (4) to give a Feedstock Mixture. The Feedstock HMFO utilized generally complies with the bulk physical and certain key chemical properties for a residual marine fuel oil otherwise compliant with ISO8217:2017 exclusive of the Environmental Contaminates. More particularly, when the Environmental Contaminate is sulfur, the concentration of sulfur in the Feedstock HMFO may be between the range of 5.0% wt. to 1.0% wt. The Feedstock HMFO should have bulk physical properties that are required of an ISO8217:2017 compliant HMFO of: a maximum kinematic viscosity at 50 C (ISO 3104) between the range from 180 mm.sup.2 / s to 700 mm.sup.2 / s and a maximum density at 15° C. (ISO 3675) between the range of 991.0 kg / m.sup.3 to 1010.0 kg / m.sup.3 and a CCAI is 780 to 870 and a flash point (ISO 2719) no lower than 60.0 C. Other properties of the Feedstock HMFO connected to the formation of particulate material (PM) include: a maximum total sediment – aged (ISO 10307-2) of 0.10 % wt. and a maximum carbon residue – micro method (ISO 10370) between the range of 18.00 % wt. and 20.00 % wt. and a maximum aluminum plus silicon (ISO 10478) content of 60 mg / kg. Potential Environmental Contaminates other than sulfur that may be present in the Feedstock HMFO over the ISO requirements may include vanadium, nickel, iron, aluminum and silicon substantially reduced by the process of the present invention. However, one of skill in the art will appreciate that the vanadium content serves as a general indicator of these other Environmental Contaminates. In one preferred embodiment the vanadium content is ISO compliant so the Feedstock MHFO has a maximum vanadium content (ISO 14597) between the range from 350 mg / kg to 450 ppm mg / kg.

[0043] 033. As for the properties of the Activating Gas, the Activating Gas should be selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseous water, and methane. The mixture of gases within the Activating Gas should have an ideal gas partial pressure of hydrogen (p.sub.H2) greater than 80% of the total pressure of the Activating Gas mixture (P) and more preferably wherein the Activating Gas has an ideal gas partial pressure of hydrogen (p.sub.H2) greater than 95 % of the total pressure of the Activating Gas mixture (P). It will be appreciated by one of skill in the art that the molar content of the Activating Gas is another criteria the Activating Gas should have a hydrogen mole fraction in the range between 80 % and 100% of the total moles of Activating Gas mixture, more preferably wherein the Activating Gas has a hydrogen mole fraction between 80 % and 99% of the total moles of Activating Gas mixture

[0044] 034. The Feedstock Mixture (i.e. mixture of Feedstock HMFO and Activating Gas) is brought up to the process conditions of temperature and pressure and introduced into a first vessel, preferably a reactor vessel, so the Feedstock Mixture is then contacted with one or more catalysts (8) to form a Process Mixture from the Feedstock Mixture.

[0045] 035. The process conditions are selected so the ratio of the quantity of the Activating Gas to the quantity of Feedstock HMFO is 250 scf gas / bbl of Feedstock HMFO to 10,000 scf gas / bbl of Feedstock HMFO; and preferably between 2000 scf gas / bbl of Feedstock HMFO; 1 to 5000 scf gas / bbl of Feedstock HMFO more preferably between 2500 scf gas / bbl of Feedstock HMFO to 4500 scf gas / bbl of Feedstock HMFO. The process conditions are selected so the total pressure in the first vessel is between of 250 psig and 3000 psig; preferably between 1000 psig and 2500 psig, and more preferably between 1500 psig and 2200 psig The process conditions are selected so the indicated temperature within the first vessel is between of 500° F. to 900 F, preferably between 650° F. and 850° F. and more preferably between 680° F. and 800° F. The process conditions are selected so the liquid hourly space velocity within the first vessel is between 0.05 oil /hour / m.sup.3 catalyst and 1.0 oil /hour / m.sup.3 catalyst; preferably between 0.08 oil /hour / m.sup.3 catalyst and 0.5 oil /hour / m.sup.3 catalyst; and more preferably between 0.1 oil /hour / m.sup.3 catalyst and 0.3 oil /hour / m.sup.3 catalyst to achieve desulfurization with product sulfur levels below 0.5 %wt..

[0046] 036. One of skill in the art will appreciate that the process conditions are determined to consider the hydraulic capacity of the unit. Exemplary hydraulic capacity for the treatment unit may be between 100 bbl of Feedstock HMFO / day and 100,000 bbl of Feedstock HMFO / day, preferably between 1000 bbl of Feedstock HMFO / day and 60,000 bbl of Feedstock HMFO / day, more preferably between 5,000 bbl of Feedstock HMFO / day and 45,000 bbl of Feedstock HMFO / day, and even more preferably between 10,000 bbl of Feedstock HMFO / day and 30,000 bbl of Feedstock HMFO / day

[0047] 037. The process may utilize one or more catalyst systems selected from the group consisting of: an ebulliated bed supported transition metal heterogeneous catalyst, a fixed bed supported transition metal heterogeneous catalyst, and a combination of ebulliated bed supported transition metal heterogeneous catalysts and fixed bed supported transition metal heterogeneous catalysts. One of skill in the art will appreciate that a fixed bed supported transition metal heterogeneous catalyst will be the technically easiest to implement and is preferred. The transition metal heterogeneous 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 consisting of alumina, alumina/boria carrier, a carrier containing metal-containing aluminosilicate, alumina/phosphorus carrier, alumina/alkaline earth metal compound carrier, 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 group 6, 8, 9 and 10 of the Periodic Table. In a preferred and illustrative embodiment, the transition metal heterogeneous catalyst is a porous inorganic oxide catalyst carrier and a transition metal catalyst, in which the preferred porous inorganic oxide catalyst carrier is alumina and the preferred transition metal catalyst is Ni—Mo, Co—Mo, Ni—W or Ni — Co—Mo

[0048] 038. The Process Mixture (10) is removed from the first vessel (8) and from being in contact with the one or more catalyst and is sent via fluid communication to a second vessel (12), preferably a gas-liquid separator or hot separators and cold separators, for separating the liquid components (14) of the Process Mixture from the bulk gaseous components (16) of the Process Mixture. The gaseous components (16) are treated beyond the battery limits of the immediate process. Such gaseous components may include a mixture of Activating Gas components and lighter hydrocarbons (mostly methane, ethane and propane but some wild naphtha) that may have been unavoidably formed as part of the by-product hydrocarbons from the process.

[0049] 039. The Liquid Components (16) are sent via fluid communication to a third vessel (18), preferably a fuel oil product stripper system, for separating any residual gaseous components (20) and by-product hydrocarbon components (22) from the Product HMFO (24). The residual gaseous components (20) may be a mixture of gases selected from the group consisting of: nitrogen, hydrogen, carbon dioxide, hydrogen sulfide, gaseous water, C1-C5 hydrocarbons. This residual gas is treated outside of the battery limits of the immediate process, 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 unavoidably formed in the process (22) may be a mixture selected from the group consisting of C5-C20 hydrocarbons (wild naphtha) (naphtha - diesel) and other condensable light liquid (C4-C8) hydrocarbons that can be utilized as part of the motor fuel blending pool or sold as gasoline and diesel blending components on the open market.

[0050] 040. The processed Product HMFO (24) is discharged via fluid communication into storage tanks beyond the battery limits of the immediate process. The Product HMFO complies with ISO8217:2017 and has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 % wt. to 1.0 % wt. preferably a sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 % wt. ppm and 0.7 % wt. and more preferably a sulfur content (ISO 14596 or ISO 8754) between the range of 0.1 % wt. and 0.5 % wt.. The vanadium content of the Product HMFO is also ISO compliant with a maximum vanadium content (ISO 14597) between the range from 350 mg / kg to 450 ppm mg / kg, preferably a vanadium content (ISO 14597) between the range of200 mg / kg and 300 mg / kg and more preferably a vanadium content (ISO 14597) between the range of 50 mg / kg and 100 mg / kg.

[0051] 041. The Feedstock HFMO should have bulk physical properties that are ISO compliant of: a maximum kinematic viscosity at 50 C (ISO 3104) between the range from 180 mm.sup.2 / s to 700 mm.sup.2 / s; a maximum density at 15 C (ISO 3675) between the range of 991.0 kg / m.sup.3 to 1010.0 kg / m.sup.3; a CCAI is in the range of 780 to 870 ; a flash point (ISO 2719) no lower than 60.0 C a maximum total sediment – aged (ISO 10307-2) of 0.10 % wt.; a maximum carbon residue – micro method (ISO 10370) between the range of 18.00 % wt. and 20.00 % wt., and a maximum aluminum plus silicon (ISO 10478) content of 60 mg / kg.

[0052] 042. The Product HMFO will have a sulfur content (ISO 14596 or ISO 8754) between 1 % and 10% of the maximum sulfur content of the Feedstock Heavy Marine Fuel Oil. That is the sulfur content of the Product will be reduced by about 80% or greater when compared to the Feedstock HMFO. Similarly, the vanadium content (ISO 14597) of the Product Heavy Marine Fuel Oil is between 1 % and 10% of the maximum vanadium content of the Feedstock Heavy Marine Fuel Oil. One of skill in the art will appreciate that the above data indicates a substantial reduction in sulfur and vanadium content indicate a process having achieved a substantial reduction in the Environmental Contaminates from the

[0053] Feedstock HMFO while maintaining the desirable properties of an ISO compliant HMFO. 043. 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, gaseous water, C1-C5 hydrocarbons. An amine scrubber will effectively remove the hydrogen sulfide content which can then be processed using technologies and processes well known to one of skill in the art. In one preferable illustrative embodiment, the hydrogen sulfide is converted into elemental sulfur using the well-known Claus process. An alternative embodiment utilizes a proprietary process for conversion of the Hydrogen sulfide to hydro sulfuric acid. Either way, the sulfur is removed from entering the environment prior to combusting the HMFO in a ships engine. The cleaned gas can be vented, flared or more preferably recycled back for use as Activating Gas.

[0054] 044. The by-product hydrocarbon components are a mixture of C5-C20 hydrocarbons (wild naphtha) (naphtha - diesel) which can be directed to the motor fuel blending pool or sold over the fence to an adjoining refinery or even utilized to fire the heaters and combustion turbines to provide heat and power to the process. These by product hydrocarbons which are the result of hydrocracking reactions should be less than 10% wt. , preferably less than 5% wt. and more preferably less than 2% wt. of the overall process mass balance.

[0055] 045. Production Plant Description: Turning now to a more detailed illustrative embodiment of a production plant, FIG. 2 shows a schematic for a production plant implementing the process described above for reducing the environmental contaminates in a Feedstock HMFO to produce a Product HMFO according to the second illustrative embodiment. An alternative embodiment for the production plant in which multiple reactors are utilized is provided in FIG. 3a and FIG. 3b within the scope of the present invention.

[0056] 046. Tables 2 and 3 provide the stream identification and equipment identification utilized in FIG. 2.

TABLE-US-00001 Stream Identifications Utilized in FIG. 2 Stream ID Name Description A Feedstock Heavy Marine Fuel Oil (HMFO) The Feedstock HMFO is a hydrocarbon stream with sulfur content greater than 10000 ppmw. Hydrocarbons range between C.sub.12 - C.sub.70+ The stream’s boiling range is between 350° F. and 1110 + °F. A' pressurized Feedstock HMFO Feedstock HMFO brought up to pressure for the process A" partially heated and pressurized Feedstock HMFO Feedstock HMFO brought up to pressure for the process and partially heated B Product HMFO The Product HMFO is a hydrocarbon stream with Sulfur Content less than 5000 ppmw. Hydrocarbons range between C.sub.12 and C.sub.70+. The stream’s boiling range is between 350° F. and 1110 + °F. C Activating Gas Activating Gas is selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseous water, and methane, with an ideal gas partial pressure of hydrogen (p.sub.H2) greater than 80% of the total pressure of the Activating Gas mixture (P) C' Activating Gas Recycle Provided from Amine Absorber and recompressed for recycle into process C" Activating Gas Make-up Provided from OSBL D Feedstock Mixture Mixture of Feedstock HMFO and Activating Gas D′ Heated Feedstock Mixture Mixture of Feedstock HMFO and Activating Gas heated to process conditions E Reactor System Effluent Product mixture from Reactor System E' partially cooled reactor System Effluent Product mixture from Reactor System F gaseous components of the Reactor System Effluent Sent to Hot Separator Vapor Air Cooler F' cooled gaseous components of the Reactor System Effluent. Gaseous stream sent to Cold Separator F" gaseous components from the Cold Separator Gaseous stream sent to Amine Absorber G liquid components of the Reactor System Effluent Hydrocarbon stream sent to Fuel Oil Product Stripper System H Cold Separator Hydrocarbon liquids Hydrocarbon stream sent to Fuel Oil Product Stripper System I Condensed liquid water from Cold Separator Sent OSBL for treatment J Lean Amine Lean Amine feeds the Amine Absorber to absorb H2S contained in the recycle hydrogen. K Rich Amine Rich Amine product from the Amine Absorber contains absorbed hydrogen sulfide. L Scrubbed Purge Gas Scrubbed Purge Gas contains hydrogen, hydrocarbons, water vapor and ppm levels of hydrogen sulfide. M Fuel Oil Stripper Vent Fuel Oil Stripper Vent contains hydrogen, hydrogen sulfide, steam and hydrocarbons sent OSBL.

TABLE-US-00002 Equipment Identifications Utilized in FIG. 2 Equipment ID Name Description 1 Oil Feed Surge Drum Vessel that receives Feedstock HMFO from OSBL and provides surge volume adequate to ensure smooth operation of the unit. 1b Feed line from Oil Feed Surge Drum to Oil Feed Pump 1c Water discharge line from Feed Surge Drum Water discharge line to OSBL 3 Oil Feed Pump Pump that delivers fuel oil at pressure required for the process. 3a Line from Oil Feed Pump to Oil Feed / Product Heat Exchanger 5 Oil Feed / Product Heat Exchanger Cross exchanger that recovers heat from the oil product to heat the oil feed. 5a Line from Oil Feed / Product Heat Exchanger to Reactor Feed / Effluent Heat Exchanger 7 Reactor Feed / Effluent Exchanger Cross exchanger that recovers heat from the reactor system effluent to the reactor feed. 7a Line from the Reactor Feed / Effluent Exchanger to the Mixing Point (X) 9 Reactor Feed Furnace Fired heater that heats reactor feed to specified reactor inlet temperature. 9a Line from Mixing Point (X) to Reactor Feed Furnace 9b Line from Reactor Feed Furnace to Reactor System 11 Reactor System System of Vessel(s) loaded with catalyst(s). 11a Line from Reactor System to Reactor Feed / Effluent Exchanger 11b Line from Reactor Feed / Effluent Exchanger to Hot Separator 13 Hot Separator Vessel receiving reactor system effluent after being cooled in Reactor Feed / Effluent Exchanger. 13a Line connecting Hot Separator to line 17b and to Hot Separator Vapor Air Cooler 13b Line from Hot Separator to Oil Product Stripper System 15 Hot Separator Vapor Air Cooler Air Cooled Heat Exchanger that cools vapor from the Hot Separator. 15a Line connecting Hot Separator Vapor Air Cooler to Cold Separator 17 Cold Separator Vessel receiving effluent from Hot Separator Vapor Air Cooler. 17a Line connecting Cold Separator to Amine Absorber 17b Line connecting Cold Separator to line 13b and Oil Product Stripper System 17c Water discharge line from Cold Separator to OSBL 19 Oil Product Stripper System Stripper Column and ancillary equipment and utilities required to remove hydrogen and hydrogen sulfide from the Product HMFO. 19a Vent stream line from Oil Product Stripper to OSBL 19b Discharge line for Product HMFO to OSBL 21 Amine Absorber Absorber Column that removes hydrogen sulfide from the vapor from the Cold Separator to form the Recycle Activating Gas stream 21a Lean Amine Feed line from OSBL 21b Rich Amine discharge line to OSBL 21c Activating Gas Recycle line from Amine Absorber to Recycle Compressor 21d Scrubbed Purge Gas Stream line to OSBL 23 Recycle Compressor For compressing recycled Activating Gas to pressure suitable for process conditions 23a Activating Gas recycle line from Recycle Compressor to Make-up Activating Gas mixing point 23b Feed line for make-up Activating Gas (C") provided OSBL connected to Activating Gas Recycle line (23a) 23c Line for conveying mixture of Recycle Activating Gas and Make-up Activating Gas to Mixing Point (X)

[0057] 047. In FIG. 2, Feedstock HMFO (A) is fed from outside the battery limits (OSBL) to the Oil Feed Surge Drum (1) that receives feed from outside the battery limits (OSBL) and provides surge volume adequate to ensure smooth operation of the unit. Water entrained in the feed is removed from the HMFO with the water being discharged a stream (1c) for treatment OSBL.

[0058] 048. The Feedstock HMFO (A) is withdrawn from the Oil Feed Surge Drum (1) via line (1b) by the Oil Feed Pump (3) and is pressurized to a pressure required for the process. The pressurized HMFO (A') then passes through line (3a) to the Oil Feed / Product Heat Exchanger (5) where the pressurized HMFO Feed (A') is partially heated by the Product HMFO (B). The Product HMFO (B) is a hydrocarbon stream with sulfur content less than 5000 ppmw and preferably less than 1000 ppmw. Hydrocarbons in the Feedstock HMFO and Product HMFO range between C.sub.12 and C70+ and the boiling range is between 350° F. and 1110 + F. The pressurized Feedstock HMFO (A') passing through line (5a) is further heated against the effluent from the Reactor System (E) in the Reactor Feed / Effluent Heat Exchanger (7).

[0059] 049. The heated and pressurized Feedstock HMFO (A") in line (7a) is then mixed with Activating Gas (C) provided via line (23c) at Mixing Point (X) to form a Feedstock Mixture (D). The mixing point (X) can be any well know gas / liquid mixing system or entrainment mechanism well known to one skilled in the art.

[0060] 050. The Feedstock Mixture (D) passes through line (9a) to the Reactor Feed Furnace (9) where the Feedstock Mixture (D) is heated to the specified process temperature. The Reactor Feed Furnace (9) may be a fired heater furnace or any other kind to type of heater as known to one of skill in the art if it will raise the temperature of the Feedstock mixture to the desired temperature for the process conditions.

[0061] 051. The fully heated Feedstock Mixture (D') exits the Reactor Feed Furnace (9) via line 9b and is fed into the Reactor System (11). The fully heated Feedstock Mixture (D') enters the Reactor System (11) where environmental contaminates, such a sulfur, nitrogen, and metals are preferentially removed from the Feedstock HMFO component of the fully heated Feedstock Mixture. The Reactor System contains a catalyst which preferentially removes the sulfur compounds in the Feedstock HMFO component by reacting them with hydrogen in the Activating Gas to form hydrogen sulfide. The Reactor System will also achieve demetalization, denitrogenation, and a certain amount of ring opening hydrogenation of the complex aromatics and asphaltenes, however minimal hydrocracking of hydrocarbons should take place. The process conditions of hydrogen partial pressure, reaction pressure, temperature and residence time as measured by time space velocity are optimized to achieve desired final product quality. A more detailed discussion of the Reactor System, the catalyst, the process conditions, and other aspects of the process are contained below in the “Reactor System Description.”

[0062] 052. The Reactor System Effluent (E) exits the Reactor System (11) via line (11a) and exchanges heat against the pressurized and partially heats the Feedstock HMFO (A′) in the Reactor Feed / Effluent Exchanger (7). The partially cooled Reactor System Effluent (E′) then flows via line (11c) to the Hot Separator (13).

[0063] 053. The Hot Separator (13) separates the gaseous components of the Reactor System Effluent (F) which are directed to line (13a) from the liquid components of the Reactor System effluent (G) which are directed to line (13b). The gaseous components of the Reactor System effluent in line (13a) are cooled against air in the Hot Separator Vapor Air Cooler (15) and then flow via line (15a) to the Cold Separator (17).

[0064] 054. The Cold Separator (17) further separates any remaining gaseous components from the liquid components in the cooled gaseous components of the Reactor System Effluent (F'). The gaseous components from the Cold Separator (F") are directed to line (17a) and fed onto the Amine Absorber (21). The Cold Separator (17) also separates any remaining Cold Separator hydrocarbon liquids (H) in line (17b) from any Cold Separator condensed liquid water (I). The Cold Separator condensed liquid water (I) is sent OSBL via line (17c) for treatment.

[0065] 055. The hydrocarbon liquid components of the Reactor System effluent from the Hot Separator (G) in line (13b) and the Cold Separator hydrocarbon liquids (H) in line (17b) are combined and are fed to the Oil Product Stripper System (19). The Oil Product Stripper System (19) removes any residual hydrogen and hydrogen sulfide from the Product HMFO (B) which is discharged in line (19b) to storage OSBL. The vent stream (M) from the Oil Product Stripper in line (19a) may be sent to the fuel gas system or to the flare system that are OSBL. A more detailed discussion of the Oil Product Stripper System is contained in the “Oil Product Stripper System Description.”

[0066] 056. The gaseous components from the Cold Separator (F") in line (17a) contain a mixture of hydrogen, hydrogen sulfide and light hydrocarbons (mostly methane and ethane). This vapor stream (17a) feeds an Amine Absorber (21) where it is contacted against Lean Amine (J) provided OSBL via line (21a) to the Amine Absorber (21) to remove hydrogen sulfide from the gases making up the Activating Gas recycle stream (C′). Rich amine (K) which has absorbed hydrogen sulfide exits the bottom of the Amine Absorber (21) and is sent OSBL via line (21b) for amine regeneration and sulfur recovery.

[0067] 057. The Amine Absorber overhead vapor in line (21c) is preferably recycled to the process as a Recycle Activating Gas (C') via the Recycle Compressor (23) and line (23 a) where it is mixed with the Makeup Activating Gas (C") provided OSBL by line (23b). This mixture of Recycle Activating Gas (C') and Makeup Activating Gas (C") to form the Activating Gas (C) utilized in the process via line (23c) as noted above. A Scrubbed Purge Gas stream (H) is taken from the Amine Absorber overhead vapor line (21c) and sent via line (21d) to OSBL to prevent the buildup of light hydrocarbons or other non-condensables.

[0068] 058. Reactor System Description: The Reactor System (11) illustrated in FIG. 2 comprises a single reactor vessel loaded with the process catalyst and sufficient controls, valves and sensors as one of skill in the art would readily appreciate.

[0069] 059. Alternative Reactor Systems in which more than one reactor vessel may be utilized in parallel as shown in FIG. 3a or in a cascading series as shown in FIG. 3b can easily be substituted for the single reactor vessel Reactor System (11) illustrated in FIG. 2. In such an embodiment in FIG. 3a, each reactor vessel (11, 12a and 12b) is similarly loaded with process catalyst and can be provided the heated Feed Mixture (D') via a common line 9b. The effluent from each of the three reactors is recombined in common line (11a) and forms a combined Reactor Effluent (E) for further processing as described above. The illustrative arrangement will allow the three reactors to carry out the process in parallel effectively multiplying the hydraulic capacity of the overall Reactor System. Control valves and isolation valves may be used to prevent feed from entering one reactor vessel (11) but not another reactor vessel (12a) or (12b). In this way one reactor (11) can be by-passed and placed off-line for maintenance and reloading of catalyst while the remaining reactors (12a) or (12b) continues to receive heated Feedstock Mixture (D'). It will be appreciated by one of skill in the art this arrangement of reactor vessels in parallel is not limited in number to three, but multiple additional reactor vessels can be added as shown by dashed line reactor (12x). The only limitation to the number of parallel reactor vessels is plot spacing and the ability to provide heated Feedstock Mixture (D') to each active reactor.

[0070] 060. In the embodiment show in FIG. 3b, cascading reactor vessels (14, 16 and 18) are loaded with process catalyst with the same or different activities toward metals, sulfur or other environmental contaminates to be removed. For example, Reactor (14) may be loaded with a highly active demetaling catalyst, reactor (16) may be loaded with a balanced demetaling / desulfurizing catalyst, and reactor (18) may be loaded with a highly active desulfurization catalyst. This allows for greater control and balance in process conditions (temperature, pressure, space flow velocity, etc...) so it is tailored for each catalyst. In this way one can optimize the parameters in each reactor depending upon the material being fed to that specific reactor / catalyst combination. and minimize the hydrocracking reactions. As with the prior illustrative embodiment, multiple cascading series of reactors can be utilized (i.e. 14 x, 16x and 18x) in parallel and in this way the benefits of such an arrangement noted above (i.e. allow one series to be “online” while the other series is “off line” for maintenance or allow increased plant capacity).

[0071] 061. The reactor(s) that form the Reactor System may be fixed bed, ebulliated bed or slurry bed or a combination of these types of reactors. As envisioned, fixed bed reactors are preferred as these are easier to operate and maintain.

[0072] 062. 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 feedstock properties, product requirements and operating constraints and optimization of the process catalyst can be carried out by routine trial and error by one of ordinary skill in the art.

[0073] 063. The process catalyst(s) comprise at least one metal selected from the group consisting of the metals each belonging to the groups 6, 8, 9 and 10 of the Periodic Table, and more preferably a mixed transition metal catalyst such as Ni—Mo, Co—Mo, Ni—W or Ni — Co— Mo are utilized. 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/boria carrier, a carrier containing metal-containing aluminosilicate, alumina/phosphorus carrier, alumina/alkaline earth metal compound carrier, alumina/titania carrier and alumina/zirconia carrier. The preferred porous inorganic oxide catalyst carrier is alumina. The pore size and metal loadings on the carrier may be systematically varied and tested with the desired feedstock and process conditions to optimize the properties of the Product HMFO. Such activities are well known and routine to one of skill in the art. Catalyst in the fixed bed reactor(s) may be dense-loaded or sock-loaded.

[0074] 064. The catalyst selection utilized within and for loading the Reactor System may be preferential to desulfurization by designing a catalyst loading scheme that results in the Feedstock mixture first contacting a catalyst bed that with a catalyst preferential to demetalization followed downstream by a bed of catalyst with mixed activity for demetalization and desulfurization followed downstream by a catalyst bed with high desulfurization activity. In effect the first bed with high demetalization activity acts as a guard bed for the desulfurization bed.

[0075] 065. The objective of the Reactor System is to treat the Feedstock HMFO at the severity required to meet the Product HMFO specification. Demetalization, denitrogenation and hydrocarbon hydrogenation reactions may also occur to some extent when the process conditions are optimized so the performance of the Reactor System achieves the required level of desulfurization. Hydrocracking is preferably minimized to reduce the volume of hydrocarbons formed as by-product hydrocarbons to the process. The objective of the process is to selectively remove the environmental contaminates from Feedstock HMFO and minimize the formation of unnecessary by-product hydrocarbons (C1-C8 hydrocarbons).

[0076] 066. The process conditions in each reactor vessel will depend upon the feedstock, the catalyst utilized and the desired final properties of the Product HMFO desired. Variations in conditions are to be expected by one of ordinary skill in the art and these may be determined by pilot plant testing and systematic optimization of the process. With this in mind it has been found that the operating pressure, the indicated operating temperature, the ratio of the Activating Gas to Feedstock HMFO, the partial pressure of hydrogen in the Activating Gas and the space velocity all are important parameters to consider. The operating pressure of the Reactor System should be in the range of 250 psig and 3000 psig, preferably between 1000 psig and 2500 psig and more preferably between 1500 psig and 2200 psig. The indicated operating temperature of the Reactor System should be 500° F. to 900 F, preferably between 650° F. and 850° F. and more preferably between 680° F. and 800 F. The ratio of the quantity of the Activating Gas to the quantity of Feedstock HMFO should be in the range of 250 scf gas / bbl of Feedstock HMFO to 10,000 scf gas / bbl of Feedstock HMFO, preferably between 2000 scf gas / bbl of Feedstock HMFO to 5000 scf gas / bbl of Feedstock HMFO and more preferably between 2500 scf gas / bbl of Feedstock HMFO to 4500 scf gas / bbl of Feedstock HMFO. The Activating Gas should be selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseous water, and methane, so Activating Gas has an ideal gas partial pressure of hydrogen (p.sub.H2) greater than 80% of the total pressure of the Activating Gas mixture (P) and preferably wherein the Activating Gas has an ideal gas partial pressure of hydrogen (p.sub.H2) greater than 95 % of the total pressure of the Activating Gas mixture (P). The Activating Gas may have a hydrogen mole fraction in the range between 80 % of the total moles of Activating Gas mixture and more preferably wherein the Activating Gas has a hydrogen mole fraction between 80% and 99% of the total moles of Activating Gas mixture. The liquid hourly space velocity within the Reactor System should be between 0.05 oil /hour / m.sup.3 catalyst and 1.0 oil /hour / m.sup.3 catalyst; preferably between 0.08 oil /hour / m.sup.3 catalyst and 0.5 oil /hour / m.sup.3 catalyst and more preferably between 0.1 oil /hour / m.sup.3 catalyst and 0.3 oil /hour / m.sup.3 catalyst to achieve desulfurization with product sulfur levels below 0.1 ppmw.

[0077] 067. The hydraulic capacity rate of the Reactor System should be between 100 bbl of Feedstock HMFO / day and 100,000 bbl of Feedstock HMFO / day, preferably between 1000 bbl of Feedstock HMFO / day and 60,000 bbl of Feedstock HMFO / day, more preferably between 5,000 bbl of Feedstock HMFO / day and 45,000 bbl of Feedstock HMFO / day, and even more preferably between 10,000 bbl of Feedstock HMFO / day and 30,000 bbl of Feedstock HMFO / day. The desired hydraulic capacity may be achieved in a single reactor vessel Reactor System or in a multiple reactor vessel Reactor System.

[0078] 068. Oil Product Stripper System Description: The Oil Product Stripper System (19) comprises a stripper column and ancillary equipment and utilities required to remove hydrogen, hydrogen sulfide and light hydrocarbons lighter than diesel from the Product HMFO. Such systems are well known to one of skill in the art a generalized functional description is provided herein. Liquid from the Hot Separator (13) and Cold Separator (7) feed the Oil Product Stripper Column (19). Stripping of hydrogen and hydrogen sulfide and light hydrocarbons lighter than diesel may be achieved via a reboiler, live steam or other stripping medium. The Oil Product Stripper System (19) may be designed with an overhead system comprising an overhead condenser, reflux drum and reflux pump or it may be designed without an overhead system. The conditions of the Oil Product Stripper may be optimized to control the bulk properties of the Product HMFO, more specifically viscosity and density.

[0079] 069. Amine Absorber System Description: The Amine Absorber System (21) comprises a gas liquid contacting column and ancillary equipment and utilities required to remove sour gas (i.e. hydrogen sulfide) from the Cold Separator vapor feed so the resulting scrubbed gas can be recycled and used as Activating Gas. Such systems are well known to one of skill in the art a generalized functional description is provided herein. Vapors from the Cold Separator (17) feed the contacting column / system (19). Lean Amine (or other suitable sour gas stripping fluids or systems) provided from OSBL is utilized to scrub the Cold Separator vapor so hydrogen sulfide is effectively removed. The Amine Absorber System (19) may be designed with a gas drying system to remove the any water vapor entrained into the Recycle Activating Gas (C').

[0080] 070. The following examples will provide one skilled in the art with a more specific illustrative embodiment for conducting the process disclosed and claimed herein:

Example 1

[0081] 071. Overview: The purpose of a pilot test run is to demonstrate that feedstock HMFO can be processed through a reactor loaded with commercially available catalysts at specified conditions to remove environmental contaminates, specifically sulfur and other contaminants from the HMFO to produce a product HMFO that is MARPOL compliant, that is production of a Low Sulfur Heavy Marine Fuel Oil (LS - HMFO) or Ultra-Low Sulfur Heavy Marine Fuel Oil (USL-HMFO).

[0082] 072. Pilot Unit Set Up: The pilot unit will be set up with two 434 cm.sup.3 reactors arranged in series to process the feedstock HMFO. The lead reactor will be loaded with a blend of a commercially available hydro-demetaling (HDM) catalyst and a commercially available hydro-transition (HDT) catalyst. One of skill in the art will appreciate that the HDT catalyst layer may be formed and optimized using a mixture of HDM and HDS catalysts combined with an inert material to achieve the desired intermediate / transition activity levels. The second reactor will be loaded with a blend of the commercially available hydro-transition (HDT) and a commercially available hydrodesulfurization (HDS). Alternatively, one can load the second reactor simply with a commercially hydrodesulfurization (HDS) catalyst. One of skill in the art will appreciate that the specific feed properties of the Feedstock HMFO may affect the proportion of HDM, HDT and HDS catalysts in the reactor system. A systematic process of testing different combinations with the same feed will yield the optimized catalyst combination for any feedstock and reaction conditions. For this example, the first reactor will be loaded with ⅔ hydro-demetaling catalyst and ⅓ hydro-transition catalyst. The second reactor will be loaded with all hydrodesulfurization catalyst. The catalysts in each reactor will be mixed with glass beads (approximately 50% by volume) to improve liquid distribution and better control reactor temperature. For this pilot test run, one should use these commercially available catalysts: HDM: Albemarle KFR 20 series or equivalent; HDT: Albemarle KFR 30 series or equivalent; HDS: Albemarle KFR 50 or KFR 70 or equivalent. Once set up of the pilot unit is complete, the catalyst can be activated by sulfiding the catalyst using dimethyldisulfide (DMDS) in a manner well known to one of skill in the art.

[0083] 073. Pilot Unit Operation: Upon completion of the activating step, the pilot unit will be ready to receive the feedstock HMFO and Activating Gas feed. For the present example, the Activating Gas can be technical grade or better hydrogen gas. The mixed Feedstock HMFO and Activating Gas will be provided to the pilot plant at rates and operating conditions as specified: Oil Feed Rate: 108.5 ml/h (space velocity = 0.25/h); Hydrogen/Oil Ratio: 570 Nm3/m3 (3200 scf/bbl); Reactor Temperature: 372° C. (702° F.); Reactor Outlet Pressure: 13.8 MPa(g) (2000 psig).

[0084] 074. One of skill in the art will know that the rates and conditions may be systematically adjusted and optimized depending upon feed properties to achieve the desired product requirements. The unit will be brought to a steady state for each condition and full samples taken so analytical tests can be completed. Material balance for each condition should be closed before moving to the next condition.

[0085] 075. Expected impacts on the Feedstock HMFO properties are: Sulfur Content (wt%): Reduced by at least 80%; Metals Content (wt %): Reduced by at least 80%; MCR / Asphaltene Content (wt %): Reduced by at least 30%; Nitrogen Content (wt %): Reduced by at least 20%; C1-Naphtha Yield (wt%): Not over 3.0% and preferably not over 1.0%.

[0086] 076. Process conditions in the Pilot Unit can be systematically adjusted as per Table 4 to assess the impact of process conditions and optimize the performance of the process for the specific catalyst and feedstock HMFO utilized.

TABLE-US-00003 Optimization of Process Conditions Case HC Feed Rate (ml/h), [LHSV( /h)] Nm.sup.3 H.sub.2/m.sup.3 oil / scf H.sub.2/bbl oil Temp (°C/°F) Pressure (MPa(g)/psig) Baseline 108.5 [0.25] 570 / 3200 372 / 702 13.8 / 2000 T1 108.5 [0.25] 570 / 3200 362 / 684 13.8/2000 T2 108.5 [0.25] 570 / 3200 382/720 13.8/2000 L1 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 S1 65.1 [0.15] 620 / 3480 385/725 15.2/2200

[0087] 077. In this way, the conditions of the pilot unit can be optimized to achieve less than 0.5% wt. sulfur product HMFO and preferably a 0.1% wt. sulfur product HMFO. Conditions for producing ULS-HMFO (i.e. 0.1% wt. sulfur product HMFO) will be: Feedstock HMFO Feed Rate: 65.1 ml/h (space velocity = 0.15/h); Hydrogen/Oil Ratio: 620 Nm.sup.3/m.sup.3 (3480 scf/bbl); Reactor Temperature: 385° C. (725° F.); Reactor Outlet Pressure: 15 MPa(g) (2200 psig)

[0088] 078. Table 5 summarizes the anticipated impacts on key properties of HMFO.

TABLE-US-00004 Expected Impact of Process on Key Properties of HMFO Property Minimum Typical Maximum Sulfur Conversion / Removal 80% 90% 98% Metals Conversion / Removal 80% 90% 100% MCR Reduction 30% 50% 70% Asphaltene Reduction 30% 50% 70% Nitrogen Conversion 10% 30% 70% C1 through Naphtha Yield 0.5% 1.0% 4.0% Hydrogen Consumption (scf/bbl) 500 750 1500

[0089] 079. Table 6 lists analytical tests to be carried out for the characterization of the Feedstock HMFO and Product HMFO. The analytical tests include those required by ISO for the Feedstock HMFO and the product HMFO to qualify and trade in commerce as ISO compliant residual marine fuels. The additional parameters are provided so that one skilled in the art will be able to understand and appreciate the effectiveness of the inventive process.

TABLE-US-00005 Analytical Tests and Testing Procedures Sulfur Content ISO 8754 or ISO 14596 or ASTM D4294 Density @ 15° C. ISO 3675 or ISO 12185 Kinematic Viscosity @ 50° C. ISO 3104 Pour 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 Number ASTM D664 Water ISO 3733 Specific Contaminants IP 501 or IP 470 (unless indicated otherwise) Vanadium or ISO 14597 Sodium Aluminum or ISO 10478 Silicon or ISO 10478 Calcium or IP 500 Zinc or IP 500 Phosphorous IP 500 Nickle Iron Distillation ASTM D7169 C:H Ratio ASTM D3178 SARA Analysis ASTM D2007 Asphaltenes, wt% ASTM D6560 Total Nitrogen ASTM D5762 Vent Gas Component Analysis FID Gas Chromatography or comparable

[0090] 080. Table 7 contains the Feedstock HMFO analytical test results and the Product HMFO analytical test results expected from the inventive process that indicate the production of a LS HMFO. It will be noted by one of skill in the art that under the conditions, the levels of hydrocarbon cracking will be minimized to levels substantially lower than 10%, more preferably less than 5% and even more preferably less than 1% of the total mass balance.

TABLE-US-00006 Analytical Results Feedstock HMFO Product HMFO Sulfur Content, mass% 3.0 0.3 Density @ 15 C, kg/m.sup.3 990 950 .sup.(1) Kinematic Viscosity @ 50 C, mm.sup.2/s 380 100 .sup.(1) Pour Point, C 20 10 Flash Point, C 110 100.sup.(1) CCAI 850 820 Ash Content, mass% 0.1 0.0 Total Sediment - Aged, 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, vol% 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 Phosphorous 2 0 Nickle 40 5 Iron 20 2 IBP 160 / 320 120 / 248 5 %wt 235 / 455 225 / 437 10 %wt 290 / 554 270/518 30 %wt 410 / 770 370 / 698 50 %wt 540 / 1004 470 / 878 70 %wt 650 / 1202 580/ 1076 90 %wt 735 / 1355 660 / 1220 FBP 820/ 1508 730 / 1346 C:H Ratio (ASTM D3178) 1.2 1.3 Saturates 16 22 Aromatics 50 50 Resins 28 25 Asphaltenes 6 3 Asphaltenes, wt% 6.0 2.5 Total Nitrogen, mg/kg 4000 3000 Note: (1) It is expected that property will be adjusted to a higher value by post process removal of light material via distillation or stripping from product HMFO.

[0091] 081. The product HMFO produced by the inventive process will reach ULS HMFO limits (i.e. 0.1% wt. sulfur product HMFO) by systematic variation of the process parameters, for example by a lower space velocity or by using a Feedstock HMFO with a lower initial sulfur content.

Example 2: RMG-380 HMFO

[0092] 082. Pilot Unit Set Up: A pilot unit was set up as noted above in Example 1 with the following changes: the first reactor was loaded with: as the first (upper) layer encountered by the feedstock 70% vol Albemarle KFR 20 series hydro-demetaling catalyst and 30% vol Albemarle KFR 30 series hydro-transition catalyst as the second (lower) layer. The second reactor was loaded with 20% Albemarle KFR 30 series hydrotransition catalyst as the first (upper) layer and 80% vol hydrodesulfurization catalyst as the second (lower) layer. The catalyst was activated by sulfiding the catalyst with dimethyldisulfide (DMDS) in a manner well known to one of skill in the art.

[0093] 083. Pilot Unit Operation: Upon completion of the activating step, the pilot unit was ready to receive the feedstock HMFO and Activating Gas feed. The Activating Gas was technical grade or better hydrogen gas. The Feedstock HMFO was a commercially available and merchantable ISO 8217: 2017 compliant HMFO, except for a high sulfur content (2.9 wt %). The mixed Feedstock HMFO and Activating Gas was provided to the pilot plant at rates and conditions as specified in Table 8 below. The conditions were varied to optimize the level of sulfur in the product HMFO material.

TABLE-US-00007 Process Conditions Product HMFO Case HC Feed Rate (ml/h), [LHSV( /h)] Nm.sup.3 H.sub.2/m.sup.3 oil / scf H.sub.2/bbl oil Temp (°C /°F) Pressure (MPa(g)/psig) Sulfur % wt. Baseline 108.5 [0.25] 570 / 3200 371 /700 13.8/2000 0.24 T1 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 L1 130.2 [0.30] 570 / 3200 372 / 702 13.8/2000 0.53 S1 65.1 [0.15] 620 / 3480 385/725 15.2 / 2200 0.10 P1 108.5 [0.25] 570 / 3200 371 / 700 / 1700 0.56 T2 / P1 108.5 [0.25] 570 / 3200 382/720 / 1700 0.46

[0094] 084. Analytical data for a representative sample of the feedstock HMFO and representative samples of product HMFO are provided below:

TABLE-US-00008 Analytical Results – HMFO (RMG-380) Feedstock Product Product Sulfur Content, mass% 2.9 0.3 0.1 Density @ 15° C., kg/m.sup.3 988 932 927 Kinematic Viscosity @ 50° C., mm.sup.2/s 382 74 47 Pour Point, °C -3 -12 -30 Flash Point, °C 116 96 90 CCAI 850 812 814 Ash Content, mass% 0.05 0.0 0.0 Total Sediment - Aged, mass% 0.04 0.0 0.0 Micro Carbon Residue, 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, vol% 0 0.0 0.0 Specific Contaminants, mg/kg Vanadium 138 15 < 1 Sodium 25 5 2 Aluminum 21 2 < 1 Silicon 16 3 1 Calcium 6 2 < 1 Zinc 5 < 1 < 1 Phosphorous <1 2 1 Nickle 33 23 2 Iron 24 8 1 IBP 178 / 352 168/334 161 / 322 5 %wt 258 / 496 235 / 455 230 / 446 10 %wt 298 / 569 270/518 264 / 507 30 %wt 395 / 743 360 / 680 351 / 664 50 %wt 517 / 962 461 / 862 439 / 822 70 %wt 633 / 1172 572 / 1062 552 / 1026 90 %wt >720 / > 1328 694 / 1281 679 / 1254 FBP >720 / > 1328 >720 / >1328 >720 / >1328 C:H Ratio (ASTM D3178) 1.2 1.3 1.3 Saturates 25.2 28.4 29.4 Aromatics 50.2 61.0 62.7 Resins 18.6 6.0 5.8 Asphaltenes 6.0 4.6 2.1 Asphaltenes, wt% 6.0 4.6 2.1 Total Nitrogen, mg/kg 3300 1700 1600

[0095] 085. As noted above in Table 7, both feedstock HMFO and product HMFO exhibited observed bulk properties consistent with ISO 8217: 2017 for a merchantable residual marine fuel oil, except that the sulfur content of the product HMFO was significantly reduced as noted above when compared to the feedstock HMFO.

[0096] 086. One of skill in the art will appreciate that the above product HMFO produced by the inventive process has achieved not only an ISO 8217:2017 compliant LS HMFO (i.e. 0.5%wt. sulfur) but also an ISO 8217:2017 compliant ULS HMFO limits (i.e. 0.1% wt. sulfur) product HMFO.

Example 3: RMK-500 HMFO

[0097] 087. The feedstock to the pilot reactor utilized in example 2 above was changed to a commercially available and merchantable ISO 8217: 2017 RMK-500 compliant HMFO, except that it has high environmental contaminates (i.e. sulfur (3.3 wt %)). Other bulk characteristic of the RMK-500 feedstock high sulfur HMFO are provide below:

TABLE-US-00009 Analytical Results- Feedstock HMFO (RMK-500) Sulfur Content, mass% 3.3 Density @ 15° C., kg/m.sup.3 1006 Kinematic Viscosity @ 50° C., mm.sup.2/s 500

[0098] 088. The mixed Feedstock (RMK-500) HMFO and Activating Gas was provided to the pilot plant at rates and conditions and the resulting sulfur levels achieved in the table below

TABLE-US-00010 Process Conditions Product (RMK-500) Case HC Feed Rate (ml/h), [LHSV( /h)] Nm.sup.3 H.sub.2/m.sup.3 oil / scf H.sub.2/bbl oil Temp (°C /°F) Pressure (MPa(g)/psig) sulfur %wt. A 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 C 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 E 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

[0099] 089. The resulting product (RMK-500) HMFO exhibited observed bulk properties consistent with the feedstock (RMK-500) HMFO, except that the sulfur content was significantly reduced as noted in the above table.

[0100] 090. One of skill in the art will appreciate that the above product HMFO produced by the inventive process has achieved a LS HMFO (i.e. 0.5%wt. sulfur) product HMFO having bulk characteristics of a ISO 8217: 2017 compliant RMK-500 residual fuel oil. It will also be appreciated that the process can be successfully carried out under non-hydrocracking conditions (i.e. lower temperature and pressure) that substantially reduce the hydrocracking of the feedstock material. It should be noted that when conditions were increased to much higher pressure (Example E) a product with a lower sulfur content was achieved, however it was observed that there was an increase in light hydrocarbons and wild naphtha production.

[0101] 091. It will be appreciated by those skilled in the art that changes could be made to the illustrative embodiments described above without departing from the broad inventive concepts thereof. It is understood, therefore, that the inventive concepts disclosed are not limited to the illustrative embodiments or examples disclosed, but it is intended to cover modifications within the scope of the inventive concepts as defined by the claims.