Multi-Stage Process and Device for Treatment Heavy Marine Fuel Oil and Resultant Composition including Microwave Promoted Desulfurization
A multi-stage process for reducing the environmental contaminants in an ISO 8217 compliant Feedstock Heavy Marine Fuel Oil involving a core desulfurizing process and a microwave treatment process 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. 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 microwave energy having a frequency selected from the group consisting of 915 MHz and 2450 MHz, in the presence of microwave absorbent material 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 reactive conditions to form a Process Mixture from said Feedstock Mixture; receiving said Process Mixture and 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.
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 mass % to 1.0 mass %.
3 . The process of claim 1 , wherein said Feedstock Heavy Marine Fuel Oil has bulk properties of: a maximum 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 %.
4 . The process of claim 1 , wherein the microwave absorbent material is selected from the group consisting of metallic oxides, sulfates, coking fines tailings; compounds containing nanostructured materials such as nanofibers and nanotubes; catalysts or mixtures of catalysts disposed of at fluid catalytic cracking units; catalysts or mixtures of catalysts disposed of at hydrotreatment units, comprised of transition metals (such as Co, Mo, Ni, etc.), supported on refractory oxides which may be chosen from among alumina, silica, titanium, zirconium and/or mixtures, used hydrodesulfurization catalysts and combinations thereof.
5 . 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/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).
6 . The process of claim 1 , wherein the reactive conditions 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.
7 . 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 catalysts under reactive conditions to form a Process Mixture from said Feedstock Mixture; receiving said Process Mixture and separating the liquid components of the Process Mixture from the bulk gaseous components of the Process Mixture; receiving said liquid components and contacting the liquid components with a microwave energy having a frequency selected from the group consisting of 915 MHz and 2450 MHz, in the presence of microwave absorbent material; subsequently separating any residual gaseous components and by-product hydrocarbon components from the Product Heavy Marine Fuel Oil; and, discharging the Product Heavy Marine Fuel Oil.
8 . The process of claim 7 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 mass % to 1.0 mass %.
9 . The process of claim 7 , wherein said Feedstock Heavy Marine Fuel Oil has bulk properties of: a maximum 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 %.
10 . The process of claim 7 , wherein the microwave absorbant material is selected from the group consisting of metallic oxides, sulfates, coking fines tailings; compounds containing nanostructured materials such as nanofibers and nanotubes; catalysts or mixtures of catalysts disposed of at fluid catalytic cracking units; catalysts or mixtures of catalysts disposed of at hydrotreatment units, comprised of transition metals (such as Co, Mo, Ni, etc.), supported on refractory oxides which may be chosen from among alumina, silica, titanium, zirconium and/or mixtures, used hydrodesulfurization catalysts and combinations thereof.
11 . The process of claim 7 , 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).
12 . The process of claim 11 , wherein the reactive conditions 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.
13 . The process of claim 10 , wherein said Product Heavy Marine Fuel Oil complies with ISO 8217 (2017) and has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.01 mass % to 1.0 mass %.
14 . The process of claim 11 , wherein said Product Heavy Marine Fuel Oil has bulk properties of: a maximum 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 %.
15 . A low sulfur heavy marine fuel composition comprising at least 50% by volume of a hydroprocessed and microwave treated residual marine fuel oil and no more than 50% by volume of Diluent Materials selected from the group consisting of: hydrocarbon materials; non-hydrocarbon materials; and, solid materials and combinations thereof.
16 . The low sulfur heavy marine fuel composition of claim 15 , wherein, the hydroprocessed and microwave treated residual marine fuel oil is compliant with ISO 8217 (2017).
17 . The low sulfur heavy marine fuel composition of claim 15 wherein the hydrocarbon materials are selected from the group consisting of: heavy marine fuel oil with a sulfur content (ISO 14596 or ISO 8754) greater than 0.5 wt; distillate based fuels; diesel; gas oil; marine gas oil; marine diesel oil; cutter oil; biodiesel; methanol, ethanol; synthetic hydrocarbons and oils based on gas to liquids technology; Fischer-Tropsch derived oils; synthetic oils based on polyethylene, polypropylene, dimer, trimer and poly butylene; atmospheric residue; vacuum residue; fluid catalytic cracker (FCC) slurry oil; FCC cycle oil; pyrolysis gas oil; cracked light gas oil (CLGO); cracked heavy gas oil (CHGO); light cycle oil (LCO); heavy cycle oil (HCO); thermally cracked residue; coker heavy distillate; bitumen; de-asphalted heavy oil; visbreaker residue; slop oils; asphaltinic oils; used or recycled motor oils; lube oil aromatic extracts; crude oil; heavy crude oil; distressed crude oil; and combination thereof; and wherein the non-hydrocarbon materials are selected from the group consisting of: residual water; detergents; viscosity modifiers; pour point depressants; lubricity modifiers; de-hazers; antifoaming agents; ignition improvers; anti rust agents; corrosion inhibitors; anti-wear additives, anti-oxidants (e.g. phenolic compounds and derivatives), coating agents and surface modifiers, metal deactivators, static dissipating agents, ionic and nonionic surfactants, stabilizers, cosmetic colorants and odorants and combination thereof; and, wherein the solid materials are selected from the group consisting of carbon or hydrocarbon solids; coke; graphitic solids; micro-agglomerated asphaltenes, iron rust; oxidative corrosion solids; bulk metal particles; paint particles; surface coating particles; plastic particles or polymeric particles or elastomer particles rubber particles; catalyst fines; ceramic particles; mineral particles; sand; clay; earthen particles; bacteria; biologically generated solids; and combination thereof.
18 . The low sulfur heavy marine fuel composition of claim 15 wherein residual marine fuel oil prior to hydroprocessing and microwave treatment has a sulfur content greater than 1.0 wt. % sulfur.
19 . The composition of claim 15 , wherein the heavy marine fuel oil composition is compliant to ISO 8217 (2017) and has a sulfur content (ISO 14596 or ISO 8754) between the range of 0.5% wt. and 0.05% wt.
20 . The composition of claim 15 , wherein the heavy marine fuel oil composition is of merchantable quality.