Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil
A multi-stage process for reducing the environmental contaminants in a ISO 8217 compliant Feedstock Heavy Marine Fuel Oil involving a core desulfurizing process and an ionic liquid extraction desulfurizing process as either a pre-treating step or post-treating step to the core process. The Product Heavy Marine Fuel Oil is compliant with ISO 8217A 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. A process plant for conducting the process is also disclosed.
1. A process for reducing the environmental contaminants in a Feedstock Heavy Marine Fuel Oil, the process comprising: contacting a Feedstock Heavy Marine Fuel Oil with a ionic liquid under extractive desulfurizing conditions to give a pre-treated Feedstock Heavy Marine Fuel Oil; mixing a quantity of the pre-treated 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 under desulfurizing conditions to form a Process Mixture from said Feedstock Mixture; receiving said Process Mixture and separating a Product Heavy Marine Fuel Oil from any gaseous components and any by-product hydrocarbon components of the Process Mixture and, discharging the Product Heavy Marine Fuel Oil.
2. The process of claim 1 wherein said Feedstock Heavy Marine Fuel Oil complies with ISO 8217:2017 and has a sulfur content (ISO 14596 or ISO 8754) between the range of 5.0% wt. to 1.0% wt.
3. The process of claim 1 , wherein said Feedstock Heavy Marine Fuel Oil has: a maximum kinematic viscosity at 50 C (ISO 3104) between the range from 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) no lower than 60.0 C and 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 vanadium content (ISO 14597) between the range from 350 mg/kg to 450 ppm mg/kg and a maximum aluminum plus silicon (ISO 10478) content of 60 mg/kg.
4. The process of claim 1 , wherein the ionic liquid is selected from the group consisting of imidazolium ionic liquids, pyridinium ionic liquids, phosphonium ionic liquids, lactamium ionic liquids, ammonium ionic liquids, pyrrolidinium ionic liquids, and combinations thereof.
5. The process of claim 4 , wherein the extractive desulfurizing conditions comprise: a temperature in the range of about 50° C. to about 500° C., a weight ratio of Heavy Marine Fuel Oil to ionic liquid in the range about 1:100 to about 100:1, and a contacting time in the range of about 1 min to about 2 hr.
6. The process of claim 1 , wherein the catalyst comprises: a porous inorganic oxide catalyst carrier and a transition metal catalyst, wherein the porous inorganic oxide catalyst carrier is at least one carrier selected from the group consisting of alumina, alumina/bona carrier, a carrier containing metal-containing aluminosilicate, alumina/phosphorus carrier, alumina/alkaline earth metal compound carrier, alumina/titania carrier and alumina/zirconia carrier, and wherein the transition metal catalyst is one or more metals selected from the group consisting of group 6, 8, 9 and 10 of the Periodic Table 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 step of contacting the Feedstock Mixture with one or more catalysts under desulfurizing conditions to form a Process Mixture from said Feedstock Mixture comprise: the ratio of the quantity of the Activating Gas to the quantity of Feedstock Heavy Marine Fuel Oil is 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 the total pressure is between of 250 psig and 3000 psig; and, the indicated temperature is between of 500° F. to 900° F., and, wherein the liquid hourly space velocity is between 0.05 oil/hour/m 3 catalyst and 1.0 oil/hour/m 3 catalyst.
8. The process of claim 1 , wherein said Product Heavy Marine Fuel Oil 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.
9. The process of claim 1 , wherein said Product Heavy Marine Fuel Oil has: a maximum kinematic viscosity at 50 C (ISO 3104) between the range from 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) no lower than 60.0 C, and 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 sulfur content (ISO 145% or ISO 8754) between the range of 0.05% wt to 1.0% wt, and a maximum vanadium content (ISO 14597) between the range from 350 mg/kg to 450 ppm mg/kg, and a maximum aluminum plus silicon (ISO 10478) content of 60 mg/kg.
10. 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 with a quantity of Activating Gas mixture to give a Feedstock Mixture; contacting the Feedstock Mixture with one or more catalysis under desulfurizing conditions to form a Process Mixture from said Feedstock Mixture; receiving said Process Mixture and separating hydrocarbon liquid components of the Process Mixture from any bulk gaseous components of the Process Mixture; receiving said hydrocarbon liquid components and contacting said hydrocarbon liquid components with a ionic liquid under extractive desulfurizing conditions; subsequently separating any residual gaseous components and any by-product hydrocarbon components from a Product Heavy Marine Fuel Oil; and, discharging the Product Heavy Marine Fuel Oil.
11. The process of claim 10 wherein said Feedstock Heavy Marine Fuel Oil complies with ISO8217:2017 and has a sulfur content (ISO 14596 or ISO 8754) between the range of 5.0% wt. to 1.0% wt.
12. The process of claim 10 , wherein said Feedstock Heavy Marine Fuel Oil has: a maximum kinematic viscosity at 50° C. (ISO 3104) between the range from 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) no lower than 60.0 C and, 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 vanadium content (ISO 14597) between the range from 350 mg/kg to 450 ppm mg/kg and a maximum aluminum plus silicon (ISO 10478) content of 60 mg/kg.
13. The process of claim 10 , wherein the ionic liquid is selected from the group consisting of imidazolium ionic liquids, pyridinium ionic liquids, phosphonium ionic liquids, lactamium ionic liquids, ammonium ionic liquids, pyrrolidinium ionic liquids, and combinations thereof.
14. The process of claim 13 , wherein the extractive desulfurizing conditions comprise: a temperature in the range of about 50° C. to about 500° C., a weight ratio of Heavy Marine Fuel Oil to ionic liquid in the range about 1:100 to about 100:1, and a contacting time in the range of about 1 min to about 2 hr.
15. The process of claim 10 , wherein the catalyst comprises: a porous inorganic oxide catalyst carrier and a transition metal catalyst, wherein 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, and wherein the transition metal catalyst is one or more metals selected from the group consisting of group 6, 8, 9 and 10 of the Periodic Table; 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).
16. The process of claim 15 , wherein the step of contacting the Feedstock Mixture with one or more catalysts under desulfurizing conditions to form a Process Mixture from said Feedstock Mixture comprise: the ratio of the quantity of the Activating Gas to the quantity of Feedstock Heavy Marine Fuel Oil is 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 the total pressure is between of 250 psig and 3000 psig; and, the indicated temperature is between of 500 F to 900 F, and, wherein the liquid hourly space velocity is between 0.05 oil/hour/m 3 catalyst and 1.0 oil/hour/m 3 catalyst.
17. The process of claim 10 , wherein said Product Heavy Marine Fuel Oil complies with ISO8217:2017 and has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.01% wt. to 1.0% wt.
18. The process of claim 17 , wherein said Product Heavy Marine Fuel Oil has: a maximum kinematic viscosity at 50° C. (ISO 3104) between the range from 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 CCA1 is in the range of 780 to 870; and a flash point (ISO 2719) no lower than 60.0° C., and 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 sulfur content (ISO 14596 or ISO 8754) between the range of 0.05% wt. to 1.0% wt., and a maximum vanadium content (ISO 14597) between the range from 350 mg/kg to 450 ppm mg/kg, and a maximum aluminum plus silicon (ISO 10478) content of 60 mg/kg.