Multi-stage process and device for treatment heavy marine fuel oil and resultant composition and the removal of detrimental solids
A multi-stage process for reducing the environmental contaminants in an ISO8217 compliant Feedstock Heavy Marine Fuel Oil involving a core desulfurizing process and a Detrimental Solids removal unit as either a pre-treating step or post-treating step to the core process. The Product Heavy Marine Fuel Oil complies 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 mass % to 1.0 mass and a Detrimental Solids content less than 60 mg/kg. A process plant for conducting the process is also disclosed.
1. A process for reducing the Environmental Contaminants and Detrimental Solids in a Feedstock Heavy Marine Fuel Oil, the process comprising: contacting a Feedstock Heavy Marine Fuel Oil, wherein the Feedstock Heavy Marine Fuel Oil is compliant with ISO 8217 (2017) Table 2 as a residual marine fuel, except for: the concentration of the Environmental Contaminates is greater than 0.5 mass %, wherein the Environmental Contaminates are selected from the group consisting of sulfur, vanadium, nickel, iron, aluminum plus silicon and combinations thereof; and, the presence of Detrimental Solids, wherein the Detrimental Solids are suspended solid particulate materials in the Feedstock Heavy Marine Fuel Oil having a diameter in the range of 1000 microns to 0.1 microns, with a Detrimental Solids Removal Unit to give a pre-treated Feedstock Heavy Marine Fuel Oil that is substantially free of the Detrimental Solids; mixing a quantity of the pre-treated Feedstock Heavy Marine Fuel Oil with a quantity of an Activating Gas mixture to give a Feedstock Mixture; contacting the Feedstock Mixture with one or more catalyst materials under reactive conditions sufficient to both: i) decrease the concentration of Environmental Contaminants to less than 0.5 mass % and ii) minimize the level of hydrocracking in the Feedstock Mixture to less than about 10% volume swell resulting from hydrocracking, forming a Process Mixture from said Feedstock Mixture wherein said Process Mixture is composed of a Product Heavy Marine Fuel Oil liquid component, gaseous components and by-product hydrocarbon components; receiving said Process Mixture and separating a Product Heavy Marine Fuel Oil liquid component 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 liquid component as a Product Heavy Marine Fuel Oil wherein the Product Heavy Marine Fuel Oil complies with ISO 8217 (2017) Table 2 as a residual marine fuel and has a maximum Environmental Contaminants content between the range of 0.01 mass % to 0.5 mass %.
2. The process of claim 1 wherein said Feedstock Heavy Marine Fuel Oil has a sulfur content (ISO 14596 or ISO 8754) between the range of 5.0 mass % to 1.0 mass %.
3. The process of claim 1 , wherein said Product Heavy Marine Fuel Oil has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.01 mass % to 0.5 mass %.
4. The process of claim 1 , wherein said Feedstock Heavy Marine Fuel Oil has: a kinematic viscosity at 50° C. (ISO 3104) between the range from 180 mm 2 /s to 700 mm 2 /s; a 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) no lower than 60° C.; a total sediment—aged (ISO 10307-2) less than 0.10 mass %; and a carbon residue—micro method (ISO 10370) less than 20.00 mass %.
5. The process of claim 1 , wherein the detrimental solids removal unit is a reactor vessel having one or more beds of a dense packed inert catalyst material.
6. The process of claim 1 , wherein the catalyst materials are selected to minimize hydrocracking under the reactive conditions and are selected from the group consisting of: a hydrodemetallization catalyst comprising one or more sulfided transition metals selected from the group consisting of group 6, 8, 9 and 10 of the Periodic Table supported on an inorganic oxide carrier; a hydrotransition catalyst comprising one or more sulfided transition metals selected from the group consisting of group 6, 8, 9 and 10 of the Periodic Table supported on an inorganic oxide carrier; a hydrodesulfurization catalyst comprising one, or more sulfided transition metals selected from the group consisting of group 6, 8, 9 and 10 of the Periodic Table supported on an inorganic oxide carrier; and wherein the Activating Gas is selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseous water, and methane, such that Activating Gas has an ideal gas partial pressure of hydrogen (p H2 ) greater than 80% of the total pressure of the Activating Gas mixture (P).
7. The process of claim 6 , wherein the reactive conditions, to minimize the level of hydrocracking in the Feedstock Mixture 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; and, 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 hr −1 and 1.0 hr −1 .
8. The process of claim 1 , wherein said Product Heavy Marine Fuel Oil has: a kinematic viscosity at 50° C. (ISO 3104) between the range from 180 mm 2 /s to 700 mm 2 /s; a 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) no lower than 60° C.; a total sediment—aged (ISO 10307-2) less than 0.10 mass %; and a carbon residue—micro method (ISO 10370) less than 20.00 mass and an aluminum plus silicon (ISO 10478) content less than 60 mg/kg.
9. The process of claim 1 wherein the Detrimental Solids Removal Unit removes the Detrimental Solids from the Feedstock, Heavy Marine Fuel Oil by physical entrainment of the Detrimental Solids and wherein the Detrimental Solids Removal Unit is comprised of one or ore solids removal element selected from the group consisting of: a porous sintered metal filter having a permeametric radii from 50 to 100 microns; a porous sintered metal filter having a permeametric radii from 50 to 0.1 microns, a packed bed of deactivated particulate alumina, a packed bed of deactivated silica, and combinations thereof.
10. A process for reducing Environmental Contaminates and Detrimental Solids 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) Table 2 as a residual marine fuel, except for: the concentration of the Environmental Contaminates is greater than 0.5 mass %, wherein the Environmental Contaminates are selected from the group consisting of sulfur, vanadium, nickel, iron, aluminum plus silicon, and combinations thereof; and, the presence of Detrimental Solids, wherein the Detrimental Solids are suspended solid particulate materials in the Feedstock Heavy Marine Fuel Oil having a diameter in the range of 1000 microns to 0.1 microns, with a quantity of Activating Gas mixture to give a Feedstock Mixture; substantially removing the Detrimental Solids from the Feedstock Mixture and; subsequently contacting the Feedstock Mixture with one or more catalyst materials under reactive conditions sufficient to both: i) decrease the concentration of Environmental Contaminants in the Feedstock Mixture to less than 0.5 mass % and ii) minimize the volume of hydrocracking to less than about 10% volume swell from hydrocracking, to form a Process Mixture from said Feedstock Mixture, wherein said Process Mixture is composed of a Product Heavy Marine Fuel Oil liquid component, a by-product hydrocarbon component, a bulk gaseous component, a residual Detrimental Solids component, and a residual gas component; directly and subsequently receiving said Process Mixture in one or more first separation vessels that are not under reactive conditions and separating the bulk gaseous components of the Process Mixture from the remaining components of the Process Mixture; directly and subsequently receiving the remaining components of the Process Mixture in one or more second separation vessels that are not under reactive conditions and separating the residual gaseous component and the by-product hydrocarbon component from the Product Heavy Marine Fuel Oil liquid component and the residual Detrimental Solids component of the Process Mixture; and subsequently passing the Product Heavy Marine Fuel Oil liquid component and the residual Detrimental Solids component of the Process Mixture into a Detrimental Solids Removal Unit to remove the residual Detrimental Solids from the Product Heavy Marine Fuel Oil liquid component of the Process Mixture, and, subsequently discharging the Product Heavy Marine Fuel Oil liquid component of the Process Mixture as a Product Heavy Marine Fuel Oil, and the Product Heavy Marine Fuel Oil complies with ISO 8217 (2017) Table 2 as a residual marine fuel and has a maximum Environmental Contaminants content between the range of 0.01 mass % to 0.5 mass %.
11. The process of claim 10 wherein said Feedstock Heavy Marine Fuel Oil has a sulfur content (ISO 14596 or ISO 8754) between the range of 5.0 mass % to 1.0 mass %.
12. The process of claim 10 , wherein said Feedstock Heavy Marine Fuel Oil has a kinematic viscosity at 50° C. (ISO 3104) between the range from 180 mm 2 /s to 700 mm 2 /s; a 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) no lower than 60° C.; a total sediment—aged (ISO 10307-2) less than 0.10 mass %; and a carbon residue—micro method (ISO 10370) less than 20.00 mass %.
13. The process of claim 10 , wherein the one or more catalyst materials are selected to minimize hydrocracking under the reactive conditions and are selected from the group consisting of: a hydrodemetallization catalyst comprising one or more sulfided transition metals selected from the group consisting of group 6, 8, 9 and 10 of the Periodic Table supported on an inorganic oxide carrier; a hydrotransition catalyst comprising one or more sulfided transition metals selected from the group consisting of group 6, 8, 9 and 10 of the Periodic Table supported on an inorganic oxide carrier; a hydrodesulfurization catalyst comprising one or more sulfided transition metals elected from the group consisting of group 6, 8, 9 and 10 of the Periodic Table supported on an inorganic oxide carrier; and wherein the Activating Gas is selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseous water, and methane, such that Activating Gas has an ideal gas partial pressure of hydrogen (p H2 ) greater than 80% of the total pressure of the Activating Gas mixture (P).
14. The process of claim 13 , wherein the reactive conditions selected to minimize the level of hydrocracking in the Feedstock Mixture 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; and, 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 hr −1 and 1.0 hr −1 .
15. The process of claim 10 , wherein said Product Heavy Marine Fuel Oil has: a of kinematic viscosity at 50° C. (ISO 3104) between the range from 180 mm 2 /s to 700 mm 2 /s; a 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) no lower than 60° C.; a total sediment—aged (ISO 10307-2) less than 0.10 mass %; and a carbon residue—micro method (ISO 10370) less than 20.00 mass %, and a aluminum plus silicon (ISO 10478) content less than 60 mg/kg.
16. The process of claim 10 wherein the Detrimental Solids Removal Unit removes the Detrimental Solids from the Product Heavy Marine Fuel Oil by physical entrainment of the Detrimental Solids and wherein the Detrimental Solids Removal Unit is comprised of one ore solids removal element selected from the group consisting of: a porous sintered metal filter having a permeametric radii from 50 to 100 microns; a porous sintered metal filter having a permeametric radii from 50 to 0.1 microns, a packed bed of deactivated particulate alumina, a packed bed of deactivated silica, and combinations thereof.
17. A process for reducing the Environmental Contaminants and the Detrimental Solids in a Feedstock Heavy Marine Fuel Oil, the process consisting of:
a. contacting a Feedstock Heavy Marine Fuel Oil with a Detrimental Solids Removal Unit to give a pre-treated Feedstock Heavy Marine Fuel Oil, wherein the Feedstock Heavy Marine Fuel Oil is compliant with ISO 8217 (2017) Table 2 as a residual marine fuel, except: the concentration of the Environmental Contaminates is greater than 0.5 mass %, and wherein the Environmental Contaminates are selected from the group consisting of sulfur, vanadium, nickel, iron, aluminum plus silicon, and combinations thereof; and, the Detrimental Solids are present, wherein the Detrimental Solids are suspended solid particulate materials in the Feedstock Heavy Marine Fuel Oil having a diameter in the range of 1000 microns to 0.1 microns;
b. subsequently mixing a quantity of the pre-treated Feedstock Heavy Marine Fuel Oil with a quantity of an Activating Gas mixture to give a Feedstock Mixture;
c. hydrodemetallization treatment of the Feedstock Mixture with one or more hydrodemetallization catalyst, materials and sending the effluent from Step c) directly to step d);
d. hydrodesulfurization treatment of the effluent from step c with one or more hydrodesulfurization catalyst materials;
wherein the combination of steps c and d form a Process Mixture from said Feedstock Mixture in the absence of hydrocracking catalyst and wherein said Process Mixture is composed of a Product Heavy Marine Fuel Oil liquid component, gaseous components and by-product hydrocarbon components and, wherein the combination of steps c and d take place in one or more reaction vessels under reactive conditions sufficient to both: i) decrease the concentration of Environmental Contaminants to less than 0.5 mass % in the Product Heavy Marine Fuel Oil liquid component, and ii) minimize the level of hydrocracking in the Product Heavy Marine Fuel Oil liquid component to less than about 10% volume swell attributable to hydrocracking;
e. directly receiving said Process Mixture from step d in at least one separation vessel and separating the Product Heavy Marine Fuel Oil liquid component of the Process Mixture from the gaseous components and by-product hydrocarbon components of the Process Mixture and,
f. discharging the Product Heavy Marine Fuel Oil liquid component from the at least one separation vessel as a Product Heavy Marine Fuel Oil to one or more storage vessels for the Product Heavy Marine Fuel Oil, wherein the Product Heavy Marine Fuel Oil complies with ISO 8217 (2017) Table 2 as a residual marine fuel and has a Environmental Contaminants content between the range of 0.01 mass % to 0.5 mass %.
18. A process for reducing the sulfur and Detrimental Solids content in a Feedstock Heavy Marine Fuel Oil, the process steps consisting of:
a. mixing a quantity of the Feedstock Heavy Marine Fuel Oil with a quantity of an Activating Gas mixture to give a Feedstock Mixture, wherein the Feedstock Heavy Marine Fuel Oil is compliant with ISO 8217 (2017) Table 2 as a residual marine fuel, except for: the concentration of sulfur is greater than 0.5 mass %; and, the Detrimental Solids are present, wherein the Detrimental Solids are suspended solid particulate materials in the Feedstock Heavy Marine Fuel Oil having a diameter in the range of 1000 microns to 0.1 microns;
b. separating the Detrimental Solids from the Feedstock Mixture to form a Feedstock Mixture substantially free from Detrimental Solids and subsequently sending the Feedstock Mixture substantially free from Detrimental Solids from b directly to c;
c. hydrodemetallization treatment of the Feedstock Mixture substantially free from Detrimental Solids with one or more hydrodemetallization catalyst materials and sending the resulting effluent from c) directly to d);
d. hydrodesulfurization treatment of the resulting effluent from c with one or more hydrodesulfurization catalyst materials and forming a Process Mixture in the absence of a hydrocracking catalyst, wherein said Process Mixture is composed of a Product Heavy Marine Fuel Oil liquid component, gaseous components, and by-product hydrocarbon components, and
wherein steps c and d take place in one or more reaction vessels under reactive conditions sufficient to both: i) decrease the concentration of sulfur to less than 0.5 mass % in the Product Heavy Marine Fuel Oil liquid component, and ii) minimize the level of hydrocracking of the Feedstock Mixture produces a less than about 10% volume swell attributable to hydrocracking in the Product Heavy Marine Fuel Oil liquid component;
e. directly receiving said Process Mixture in at least one separation vessel not under reactive conditions and separating the Product Heavy Marine Fuel Oil liquid component of the Process Mixture from the gaseous components and by-product hydrocarbon components of the Process Mixture and,
f. discharging the Product Heavy Marine Fuel Oil liquid component from the at least one separation vessel as a Product Heavy Marine Fuel Oil to one or more storage vessels for the Product Heavy Marine Fuel Oil, wherein the Product Heavy Marine Fuel Oil complies with ISO 8217 (2017) Table 2 as a residual marine fuel and has a sulfur content between the range of 0.01 mass % to 0.5 mass %.