Multi-Stage Process and Device for Reducing Environmental Contaminates in Heavy Marine Fuel Oil
20190233741 · 2019-08-01
Assignee
Inventors
- Michael Joseph Moore (Houston, TX, US)
- Bertrand Ray Klussmann (Houston, TX, US)
- Carter James White (Houston, TX, US)
Cpc classification
B01J8/0292
PERFORMING OPERATIONS; TRANSPORTING
C10G25/003
CHEMISTRY; METALLURGY
C10G2300/4062
CHEMISTRY; METALLURGY
C10G2300/30
CHEMISTRY; METALLURGY
C10G45/08
CHEMISTRY; METALLURGY
C10L2200/0438
CHEMISTRY; METALLURGY
B01J8/0457
PERFORMING OPERATIONS; TRANSPORTING
C10G2300/1044
CHEMISTRY; METALLURGY
C10G45/22
CHEMISTRY; METALLURGY
C10L1/1608
CHEMISTRY; METALLURGY
C10G45/02
CHEMISTRY; METALLURGY
B01J2208/00557
PERFORMING OPERATIONS; TRANSPORTING
C10G45/06
CHEMISTRY; METALLURGY
C10L2200/0438
CHEMISTRY; METALLURGY
C10L2270/026
CHEMISTRY; METALLURGY
B01D53/1481
PERFORMING OPERATIONS; TRANSPORTING
C10L1/1608
CHEMISTRY; METALLURGY
C10G67/06
CHEMISTRY; METALLURGY
C10G45/00
CHEMISTRY; METALLURGY
C10G2300/1059
CHEMISTRY; METALLURGY
C10G2300/107
CHEMISTRY; METALLURGY
C10G2300/208
CHEMISTRY; METALLURGY
B01J2208/025
PERFORMING OPERATIONS; TRANSPORTING
B01J8/008
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
A multi-stage process for reducing the environmental contaminants in a ISO8217 compliant Feedstock Heavy Marine Fuel Oil involving a core desulfurizing process and an Oxidative 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.
Claims
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 oxidizing agent under oxidative 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 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: 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 in the range of 780 to 870 and a flash point (ISO 2719) no lower than 60.0 C and a maximum total sedimentaged (ISO 10307-2) of 0.10 mass % and a maximum carbon residuemicro method (ISO 10370) between the range of 18.00 mass % and 20.00 mass % 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 oxidizing agent is selected from the group consisting of a gaseous oxidant, an organic oxidant, an inorganic oxidant, a bio-oxidant or combinations of these.
5. The process of claim 4, wherein the oxidative desulfurizing conditions include the steps of: contacting the HMFO material with the oxidizing agent to form a HMFO containing oxidized sulfur compounds and separating the HMFO from the oxidized sulfur compounds using a process selected from the group consisting of: thermal decomposition, polar solvent extraction, aqueous caustic wash; selective absorption onto solid absorptive materials and combinations thereof.
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/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.sub.H2) greater than 80% of the total pressure of the Activating Gas mixture (P).
7. The process of claim 6, wherein the hydrodesulfurization 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.sup.3 catalyst and 1.0 oil/hour/m.sup.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 mass % to 1.0 mass
9. The process of claim 8, wherein said Product Heavy Marine Fuel Oil has: 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 in the range of 780 to 870; and a flash point (ISO 2719) no lower than 60.0 C, and a maximum total sedimentaged (ISO 10307-2) of 0.10 mass %, and a maximum carbon residuemicro method (ISO 10370) between the range of 18.00 mass % and 20.00 mass %, and a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 mass % to 1.0 mass %, 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 catalysts under desulfuring 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 oxidizing agent under oxidative desulfurizing conditions; 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.
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 mass % to 1.0 mass %
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.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 in the range of 780 to 870 and a flash point (ISO 2719) no lower than 60.0 C and a maximum total sedimentaged (ISO 10307-2) of 0.10 mass % and a maximum carbon residuemicro method (ISO 10370) between the range of 18.00 mass % and 20.00 mass % 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 oxidizing agent is selected from the group consisting of a gaseous oxidant, an organic oxidant, an inorganic oxidant, a bio-oxidant or combinations of these.
14. The process of claim 13, wherein the oxidative desulfurizing conditions include the steps of: contacting the HMFO material with the oxidizing agent to form a HMFO containing oxidized sulfur compounds and separating the HMFO from the oxidized sulfur compounds using a process selected from the group consisting of: thermal decomposition, polar solvent extraction, aqueous caustic wash; selective absorption onto solid absorptive materials and combinations thereof.
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.sub.m) greater than 80% of the total pressure of the Activating Gas mixture (P).
16. The process of claim 15, wherein the hydrodesulfurization 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.sup.3 catalyst and 1.0 oil/hour/m.sup.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 mass % to 1.0 mass %
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.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 in the range of 780 to 870; and a flash point (ISO 2719) no lower than 60.0? C., and a maximum total sedimentaged (ISO 10307-2) of 0.10 mass %, and a maximum carbon residuemicro method (ISO 10370) between the range of 18.00 mass % and 20.00 mass %, and a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 mass % to 1.0 mass %, 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.
Description
DESCRIPTION OF DRAWINGS
[0027]
[0028]
[0029]
[0030] IG. 4 is a basic schematic diagram of a plant to produce Product HMFO utilizing a combination of a oxidative desulfurizing process to pre-treat the feedstock HMFO and a subsequent core process to produce Product HMFO.
[0031]
DETAILED DESCRIPTION
[0032] 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:
[0033] 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.
[0034] 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.
[0035] 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.
[0036] 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.
[0037] Activating Gas: is a mixture of gases utilized in the process combined with the catalyst to remove the environmental contaminates from the Feedstock HMFO.
[0038] 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).
[0039] 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.
[0040] 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.
[0041] Bpd: is an abbreviation for Bbl per day.
[0042] 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).
[0043] The inventive concepts are illustrated in more detail in this description referring to the drawings, in which
[0044] 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
[0045] 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.
[0046] The core 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/catalyst; and more preferably between 0.1 oil/hour/m.sup.3 catalyst and 0.3 oil/hour/m.sup.3 catalyst to achieve deep desulfurization with product sulfur levels below 0.1 ppmw.
[0047] One of skill in the art will appreciate that the core 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
[0048] The core 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 NiMo, CoMo, NiW or NiCoMo
[0049] The Process Mixture (10) in this core process 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.
[0050] The Liquid Components (16) in this core process 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) (naphthadiesel) 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.
[0051] The Product HMFO (24) resulting from the core process 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 mass % to 1.0 mass % preferably a sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 mass % ppm and 0.7 mass % and more preferably a sulfur content (ISO 14596 or ISO 8754) between the range of 0.1 mass % and 0.5 mass %. 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.
[0052] 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 sedimentaged (ISO 10307-2) of 0.10 mass %; a maximum carbon residuemicro method (ISO 10370) between the range of 18.00 mass % and 20.00 mass %, and a maximum aluminum plus silicon (ISO 10478) content of 60 mg/kg.
[0053] 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 Feedstock HMFO while maintaining the desirable properties of an ISO compliant HMFO.
[0054] 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, light 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.
[0055] The by-product hydrocarbon components are a mixture of C5-C20 hydrocarbons (wild naphtha) (naphthadiesel) 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.
[0056] The Product HMFO (24) is discharged via fluid communication into storage tanks beyond the battery limits of the immediate process.
[0057] Oxidative Desulfurizing Process: It will be appreciated by one of skill in the art, that the conditions utilized in the core process have been intentionally selected to minimize cracking of hydrocarbons, but at the same time remove significant levels of sulfur from the Feedstock HMFO. However, one of skill in the art will also appreciate that there may be certain hard sulfur compounds present in the Feedstock HMFO removal of which would require elevated temperatures, increased hydrogen pressures, longer residence times for removal all of which would tend to cause cracking of hydrocarbons and an adverse impact upon the desirable bulk properties of the Product HMFO. Process and systems for the removal of these hard sulfur compounds may be required to achieve an ultra-low sulfur (i.e. sulfur content (ISO 14596 or ISO 8754) less than 0.1% wt. and preferably lower than 0.05% wt. sulfur content (ISO 14596 or ISO 8754)) Product HMFO. These processes and systems must achieve this without substantially altering the desirable bulk properties (i.e. compliance with ISO 8217:2017 exclusive of sulfur content) of the Product HMFO
[0058] In the following description, items already described above as part of the core process have retained the same numbering and designation for ease of description. As show in
[0059] In an embodiment of the present invention, the HMFO stream is contacted with an oxidant to convert the organo-sulfur compounds into oxidized organo-sulfur compounds such as sulfones and sulfoxides. The resulting HMFO stream containing the oxidized sulfur compounds can then be separated from the oxidizing agent (i.e. by physical separation or decomposition of any residual oxidizing agent) and followed by removal of the oxidized organo-sulfur compounds. This last step may involve extractive contact with a selective solvent having a greater selectivity for the oxidized sulfur compounds than for the HMFO to produce a solvent containing at least a portion of the oxidized sulfur compounds and a HMFO stream having a reduced concentration of oxidized sulfur compounds; or alternatively it may simply involve heating the HMFO stream containing the oxidized sulfur compounds to cause the thermal decomposition of the sulfones and sulfoxides to gaseous sulfur compounds (i.e. hydrogen sulfide and/or sulfur dioxides) and residual hydrocarbon materials which are readily separated/treated using known methods.
[0060] Turning now to the oxidizing agent material utilized in the oxidative desulfurizing unit 3, a number of oxidizing agents may be useful in the first or oxidative desulfurization step. The oxidizing agent may be selected from the group consisting of a gaseous oxidant, an organic oxidant, an inorganic oxidant, a bio-oxidant or combinations of these. When used in combination, a mixture of two oxidizing agents may be used in the same reactor, for example, gaseous oxidant (ozone or oxygen) and organic oxidizing agent or inorganic oxidizing agent. Alternatively, the different oxidizing agents can be utilized in a cascading series of reactors that are complimentary to each other. For example, an initial stage of may be conducted using a bio-oxidizing agent and a subsequent stage with a stronger oxidizing agent (i.e. gaseous oxidant, an organic oxidant, an inorganic oxidant, or combinations of these). For example, the combination of Ozone and t-butylhydroperoxide as a pair of oxidizing agents is utilized to oxidize sulfur compounds in diesel as disclosed in U.S. Pat. No. 9,365,780 (the contents of which are incorporated herein by reference). Optimization of the process and compatibility aspects can be determined by one of skill in the art by routine and systematic testing of HMFO material and oxidizing agents.
[0061] In one embodiment, the oxidizing agent can be a gaseous oxidant selected from the group consisting ozone, nitrogen oxides, molecular oxygen, air, oxygen depleted air (i.e. air in which the concentration of oxygen can be less than about 21 vol. %). When oxygen is utilized, it may be desirable to include a promoter material such as metal from group 5A and Group 8 of the Periodic Table or their salts or oxides, more specifically platinum, palladium, nickel and vanadium. These promotor materials are preferably supported on suitable materials, for example alumina, silica or activated carbon. Where the support material has cracking tendencies, such as alumina, the support material may be first treated with alkali metal hydroxides or ammonia compounds to deactivate the support. One of skill in the art will appreciate that the use of such promotors will improve the selective oxidation step in a shorter time period and/or lower temperature and milder conditions. In one embodiment, the oxidizing step is conducted in a temperature range of 80? C. to 180? C., conditions under which the HMFO is sufficiently fluid like to be pumped, stirred, etc. . . . and the amount of gaseous oxidant is in the range of 1 and 6 active oxygen equivalents to each sulfur molecule equivalents in the feedstock. Preferably when oxygen or air is utilized, the temperature will lie between the range of 130? C. and 180? C. and the reaction period will be between 2 hours and 20 hours.
[0062] In another embodiment the oxidizing agent can be an organic oxidant selected from the group consisting of alkyl hydroperoxides, such as tert-butyl hydroperoxide (TBHP), cumyl hydroperoxide (CHP) and/or ethylbenzene hydroperoxide (EBHP); peroxides, such as kerosene peroxide; percarboxylic acids, such as peracetic acid. In some instances when an organic oxidizing agent is utilized, a suitable catalyst which is capable of reacting sulfur compounds and organic oxidizing agent to produce sulfones may be utilized. A preferred suitable catalyst when alkyl hydroperoxides are utilized may be selected from the group consisting of: heterogeneous titanium(IV) catalyst having the general formula Ti(OOR)(OH)(OR).sub.2; R is selected from the group consisting of hydride, alkyl groups, aryl groups, and/or alkylaryl groups; and wherein R is selected from the group consisting of ethylene glycol, glycerol, sorbitol, xylitol and/or mixtures thereof; a molybdenum compound, such as MoO.sub.3, MgMoO.sub.4 supported on an inorganic oxide support such as alumina, silica, MgO, ZrO.sub.2 and ZnO. When such combinations are utilized, the operating conditions in the organic sulfur oxidation zone can include a pressure from about 100 kPa (0 psig) to about 3550 kPa (500 psig) and a temperature from about 49? C. (120? F.) to about 180? C. (356? F.).
[0063] In another embodiment the oxidizing agent can be an inorganic oxidant is selected from the group consisting of aqueous ferrate solution, aqueous permanganate solution. In such an embodiment, simple contacting of the HMFO with an aqueous solution of the oxidizing agent will be sufficient to cause the oxidation of the organo sulfur compounds. However, this must be done under carefully controlled circumstances to avoid excess oxidizing agent being present and potentially adversely impacting the non-sulfur containing components of the HMFO. A counter-current reactor may be useful in these instances as it will limit the contact time and allow the careful control and monitoring of the concentration of oxidizing agent relative to the on-line measured concentration of sulfur compounds. That is to say the control system should be able to automatically monitor the level of sulfur compounds present in the feed HMFO on a real-time or nearly real time basis and use this data to adjust the amount of oxidizing agent introduced into the reactor. Similar feed properties/reactant feed level control loops are well known to and well within the abilities of one of skill in the art to implement.
[0064] In another embodiment the oxidizing agent can be a bio-oxidizing agent in aqueous solution such as a microorganisms selected from the group which is capable of a selective oxidation of the sulfur in organic sulfur compounds, to the sulfoxide and/or sulfone form, without concomitant oxidation of other components of the HMFO. Microorganisms known to perform selective sulfur oxidation include Rhodococcus (previously identified as Arthrobacter) strains ATCC 55309 and ATCC 55310 (U.S. Pat. No. 5,607,857), Rhodococcus rhodochrous strain ATCC 53968 (U.S. Pat. No. 5,104,801) Bacillus sphaericus strain ATCC 53969 (U.S. Pat. No. 5,002,888), Rhodococcus erythropolis strains N1-36 and D-1 (Wang, P. and Krawiec, S. (1994); microorganisms reported to desulfurization of dibenzothiophene to 2-hydroxybiphenyl. Arch. Microbiol. 161, 266-271, Izumi, Y., Ohshiro, T., Ogino, H., Hine, Y. and Shimao, M. (1994); selective desulfurization of dibenzothiophene by Rhodococcus erythropolis D-1. Appl. Environ. Microbiol. 60, 223-226); Corynebacterium strain SY1 (Omori, T., Monna, L., Saiki, Y., and Kodama, T. (1992); desulfurization of dibenzothiophene by Corynebacterium sp. Stain SY1. App. Envir. Micro. 58, 911-915) and Brevibacterium strain DO (van Afferden, M., Schacht, S., Klein, J. and Truper, H. G. (1990); ?radation of dibenzothiophene by Brevibacterium sp. DO. Arch. Microbiol. 153, 324-328). Preferable examples include Rhodococcus species ATCC 55309, Rhodococcus species ATCC 55310, or combinations thereof. When a bio-oxidizing agent is utilized the HMFO material to be desulfurized will be at mild temperatures (0-100? C.), in the presence of oxygen, brought into contact with the biocatalysts (either whole cell, cell fraction, or enzyme preparation), contained within an aqueous buffer containing mineral salts, and if required a carbon, nitrogen and phosphorous source, and if required cofactors (e.g., NAD(P)H), for a sufficiently long period of time to allow the conversion of all, or part of, the organic sulfur into the corresponding sulfoxides and sulfones. Following the bio-oxidation step, the treated HMFO is separated from the biocatalysts, by any of a variety of standard techniques including gravity separation, gravity separation facilitated by heating, gravity separation facilities by an applied electrical potential (as in crude oil electrostatic desalters), and centrifugation. Alternatively, the bio-oxidizing agent may be immobilized in a gel or solid support, in which case the HMFO will be brought in contact with the bio-oxidizing agent and subsequently separated via an outlet port from the reactor without the need for further separation steps. Depending upon the nature of any subsequent process for removal of the oxidized sulfur compounds, separation of water and/or water bio-oxidizing agent from the HMFO may not be required. For example, if thermal decomposition is utilized, the heat will not only decompose the oxidized sulfur compounds, but also effectively remove and/or sterilize the HMFO of any active microbial content.
[0065] Following the oxidative desulfurization step, the sulfones and sulfoxides will be removed from the HMFO material. A range of potential removal processes are known in the art including: thermal decomposition; solvent extraction; caustic wash; contact with solid absorbents, each of which is described below. One of skill in the art will appreciate that one or more of these methods may be utilized to achieve the optimal removal of the oxidized sulfur compounds from the HMFO, it is contemplated that a combinations of these steps may be utilized. As noted above, while simplistically shown in the Figures, the removal of the oxidized sulfur compounds from the HMFO may involve stirred tank reactors, thermal reactors, liquid solid separators such centrifuges or settling tanks, concurrent or counter current contacting or extraction processes all of which are conventional and readily apparent to one of skill in the art of chemical and refining processes based on routine lab scale pilot testing.
[0066] In one embodiment thermal decomposition may be utilized subsequent to the oxidative desulphurization step. Preferably this step is carried out at temperatures above, 200? C. and preferably above 250? C. and more preferably in the 300-400? C. range. Under these conditions the oxidized sulfur compounds are thermally decomposed into organic components (mostly aliphatic and aromatic hydrocarbons) and gaseous sulfur compounds, such as sulfur dioxide or hydrogen sulfide. The thermal decomposition step may be carried out in the presence of promoter materials such as ferric oxide on alumina, bauxite, silica, silica-alumina and the like. A small amount of inert carrier gas may be utilized to ?as the HMFO and remove the gaseous sulfur components being liberated. In one such embodiment, the thermal decomposition takes place at the same time as the by-product hydrocarbons (i.e. lights and wild naphtha) and other entrained gases are separated from the Product HMFO. In another embodiment a tube furnace or similar heated flow through reactor will be utilized to allow for a continuous operation and flow of HMFO material. One of skill in the art will appreciate that the generation of sulfur dioxides and/or hydrogen sulfide will require scrubbers to prevent the emissions of such compounds into the environment. Such systems are well known to one of skill in the art and need to be described in detail herein.
[0067] In another illustrative embodiment, solvent extraction using polar organic fluids such as methanol, acetone, acetonitrile, dimethylformamide (DMF) or similar fluids that are not generally soluble in HMFO can be utilized in removing oxidized sulfur compounds from the HMFO. Selection of the appropriate polar extraction fluid will be simply a matter of lab testing to determine the optimal extraction fluid. In one embodiment, it is expected that methanol will be the most economical and useful organic polar fluids for extracting the oxidized sulfur compounds from the HMFO. In another alternative embodiment, ionic liquids may be utilized as the extraction medium. Generally, ionic liquid materials are non-aqueous, organic salts composed of a cation and an anion. These materials have relatively low melting points when compared to ionic solids (such a table salt or other common ionic solids), often below 100? C., undetectable vapor pressure, and good chemical and thermal stability. The cationic charge of the salt is localized over hetero atoms, such as nitrogen, phosphorous, and sulfur and the anions may be any inorganic, organic, or organometallic species. The benefits of the ionic liquid extraction technology for the extraction of the oxidized sulfur compounds from the HMFO are very mild process conditions (i.e. conditions that do not alter the bulk properties of the ISO 8217 2017 compliant feedstock HMFO), high efficiency in removal of oxidized sulfur compounds from the HMFO, and an environmental benign process. An ionic liquid can be selected from the group liquid and semi-liquid salts having the general formula Q+ A? wherein Q+ (also known as the cationic component) for example quaternary ammonium cations and quaternary phosphonium cations and A? represents the anionic component which may be any anion that forms a liquid or semi-liquid salt at or below the temperature used in the extraction step which should be preferably below 300? C. and more preferably below about 100? C. A wide range of ionic liquids may be useful in extracting oxidized sulfur compounds from the HMFO including but not limited to ionic liquids consists essentially of imidazolium ionic liquids, pyridinium ionic liquids, phosphonium ionic liquids, lactamium ionic liquids, ammonium ionic liquids, pyrrolidinium ionic liquids, and combinations thereof. In still another embodiment, 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. Imidazolium, pyridinium, lactamium, ammonium, and pyrrolidinium ionic liquids have a cation comprising at least one nitrogen atom. Phosphonium ionic liquids have a cation comprising at least one phosphorous atom. This extraction process utilizing either polar organic liquids or ionic liquids may be conducted using batch extraction, concurrent or counter current extraction techniques well known to one of skill in the art. Regeneration or recovery of the extracting liquid will depend upon the nature of the fluid utilized, however with methanol a simple distillation may be useful and with ionic liquids regeneration by exposure to a reducing environment such a hydrogen gas followed by separation may be utilized.
[0068] In another embodiment, an aqueous caustic containing wash fluid contacts the oxidized HMFO with caustic inorganic oxides (alkali oxides and hydroxides) which may be dissolved or supported on inert supports. The contact between the oxidized HMFO and the caustic aqueous solution may be facilitated by contacting caustic with hanging fiber barrier (such as that disclosed in U.S. Pat. No. 8,574,429, the contents of which are incorporated herein by reference), capillary tubes, or microemulsion blender/contactor all of which are known to one of skill in the art of mixing aqueous solutions with heavy/viscous hydrocarbons. In such instances, it may be desirable to include a phase transfer agent such as polyol or other similar surfactant utilized in the water washing of crude oil in a desalter. Alternatively, the caustic material can be immobilized and supported on an inert material such as caustic treated alumina or silica.
[0069] In another illustrative embodiment, absorbents which selectively adsorb sulfones and sulfoxides may also be utilized to remove the oxidized sulfur compounds from the HMFO in the process of the present invention. Preferred adsorbents include silica gel, zeolites and alumina. Preferred operating conditions in an adsorption zone include a pressure from about 100 kPa (14.7 psig) to about 3550 kPa (500 psig) and a temperature from about 40? C. (104? F.) to about 200? C. (392? F.). Regeneration of spent adsorbent containing sulfones is preferably conducted by contacting the spent adsorbent with a suitable desorbant including pentane, hexane, benzene, toluene, xylene and admixtures thereof, for example. Once the sulfone is removed from the spent adsorbent, the regenerated adsorbent containing a reduced level of sulfone may be reused to adsorb additional sulfone. The flow of streams may be up flow or down flow through vessels.
[0070] Without regard to the type of oxidizing agent/removal process utilized in the oxidative desulfurizing unit, the fluid effluent from oxidative desulfurizing unit 3 need not have all or even substantially all of the sulfur compounds in the HMFO feed removed. Rather the concept is remove at least a portion of the sulfur compounds to reduce the overall sulfur load on the subsequent process units. In this way one may be able to achieve a level of sulfur reduction for a HMFO not previously achieved while at the same time minimizing the cracking of hydrocarbons and maintaining the desirable bulk properties of the HMFO. In one illustrative embodiment, the fluid effluent from oxidative desulfurizing unit 3 preferably contains less than about 90 weight percent of the amount of sulfur in the fluid feed charged to oxidative desulfurizing unit 3, more preferably less than about 75 weight percent of the amount of sulfur in the fluid feed, and most preferably less than 50 weight percent of the amount of sulfur in the fluid feed.
[0071] An alternative illustrative embodiment is shown in
[0072] Product HMFO The Product HFMO resulting from the disclosed illustrative process is of merchantable quality for sale and use as a heavy marine fuel oil (also known as a residual marine fuel oil or heavy bunker fuel) and exhibits the bulk physical properties required for the Product HMFO to be an ISO compliant (i.e. ISO8217:2017) residual marine fuel oil exhibiting the bulk properties 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 sedimentaged (ISO 10307-2) of 0.10% wt.; a maximum carbon residuemicro 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.
[0073] The Product HMFO has a sulfur content (ISO 14596 or ISO 8754) less than 0.5 wt % and preferably less than 0.1% wt. and is fully compliant with the IMO Annex VI (revised) requirements for a low sulfur and preferably an ultra-low sulfur HMFO. That is the sulfur content of the Product HMFO has been reduced by about 90% or greater when compared to the Feedstock HMFO. Similarly, the vanadium content (ISO 14597) of the Product Heavy Marine Fuel Oil is less than 10% and more preferably less than 1% of the maximum vanadium content of the Feedstock Heavy Marine Fuel Oil. One of skill in the art will appreciate that a substantial reduction in sulfur and vanadium content of the Feedstock HMFO indicates a process having achieved a substantial reduction in the Environmental Contaminates from the Feedstock HMFO; of equal importance is that this has been achieved while maintaining the desirable properties of an ISO8217:2017compliant HMFO.
[0074] The Product HMFO not only complies with ISO8217:2017 (and is merchantable as a residual marine fuel oil or bunker fuel), the Product HMFO 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 0.5% 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 well within the maximum vanadium content (ISO 14597) required for an ISO8217:2017 residual marine fuel oil exhibiting a vanadium content lower than 450 ppm mg/kg, preferably a vanadium content (ISO 14597) lower than 300 mg/kg and more preferably a vanadium content (ISO 14597) between the range of 50 mg/kg and 100 mg/kg.
[0075] One knowledgeable in the art of marine fuel blending, bunker fuel formulations and the fuel logistical requirements for marine shipping fuels will readily appreciate that without further compositional changes or blending, the Product HMFO can be sold and used as a low sulfur MARPOL Annex VI compliant heavy (residual) marine fuel oil that is a direct substitute for the high sulfur heavy (residual) marine fuel oil or heavy bunker fuel currently in use. One illustrative embodiment is an ISO8217:2017 compliant low sulfur heavy marine fuel oil comprising (and preferably consisting essentially of) a 100% hydroprocessed ISO8217:2017 compliant high sulfur heavy marine fuel oil, wherein the sulfur levels of the hydroprocessed ISO8217:2017 compliant high sulfur heavy marine fuel oil is greater than 0.5% wt. and wherein the sulfur levels of the ISO8217:2017 compliant low sulfur heavy marine fuel oil is less than 0.5% wt. Another illustrative embodiment is an ISO8217:2017 compliant ultra-low sulfur heavy marine fuel oil comprising (and preferably consisting essentially of) a 100% hydroprocessed ISO8217:2017 compliant high sulfur heavy marine fuel oil, wherein the sulfur levels of the hydroprocessed ISO8217:2017 compliant high sulfur heavy marine fuel oil is greater than 0.5% wt. and wherein the sulfur levels of the ISO8217:2017 compliant low sulfur heavy marine fuel oil is less than 0.1% wt.
[0076] As a result of the present invention, multiple economic and logistical benefits to the bunkering and marine shipping industries can be realized. More specifically the benefits include minimal changes to the existing heavy marine fuel bunkering infrastructure (storage and transferring systems); minimal changes to shipboard systems are needed to comply with emissions requirements of MARPOL Annex VI (revised); no additional training or certifications for crew members will be needed, amongst the realizable benefits. Refiners will also realize multiple economic and logistical benefits, including: no need to alter or rebalance the refinery operations and product streams to meet a new market demand for low sulfur or ultralow sulfur HMFO; no additional units are needed in the refinery along with accompanying additional hydrogen or sulfur capacity because the illustrative process can be conducted as a standalone unit; refinery operations can remain focused on those products that create the greatest value from the crude oil received (i.e. production of petrochemicals, gasoline and distillate (diesel); refiners can continue using the existing slates of crude oils without having to switch to sweeter or lighter crudes to meet the environmental requirements for HMFO products; to name a few.
[0077] Heavy Marine Fuel Composition One aspect of the present inventive concept is a fuel composition comprising, but preferably consisting essentially of, the Product HMFO resulting from the processes disclosed, and may optionally include Diluent Materials. As noted above, the bulk properties of the Product HMFO itself complies with ISO8217:2017 and meets the global IMO Annex VI requirements for maximum sulfur content (ISO 14596 or ISO 8754). To the extent that ultra-low levels of sulfur are desired, the process of the present invention achieves this and one of skill in the art of marine fuel blending will appreciate that a low sulfur or ultra-low sulfur Product HMFO can be utilized as a primary blending stock to form a global IMO Annex VI compliant low sulfur Heavy Marine Fuel Composition. Such a low sulfur Heavy Marine Fuel Composition will comprise (and preferably consist essentially of): a) the Product HMFO and b) Diluent Materials. In one embodiment, the majority of the volume of the Heavy Marine Fuel Composition is the Product HMFO with the balance of materials being Diluent Materials. Preferably, the Heavy Maine Fuel Composition is at least 75% by volume, preferably at least 80% by volume, more preferably at least 90% by volume, and furthermore preferably at least 95% by volume Product HMFO with the balance being Diluent Materials.
[0078] Diluent Materials may be hydrocarbon or non-hydrocarbon based materials that are mixed into or combined with or added to, or solid particle materials that are suspended in, the Product HMFO. The Diluent Materials may intentionally or unintentionally alter the composition of the Product HMFO but not in a way that the resulting mixture fails to comply with the ISO 8217 (2017) standards for the bulk properties of residual marine fuels or fails to have a sulfur content lower than the global MARPOL standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754). Examples of Diluent Materials that are considered to be hydrocarbon based materials include: Feedstock HMFO (i.e. high sulfur HMFO); distillate based fuels such as road diesel, gas oil, MGO or MDO; cutter oil (which is currently used in formulating residual marine fuel oils); renewable oils and fuels such as biodiesel, methanol, ethanol, and the like; synthetic hydrocarbons and oils based on gas to liquids technology such as Fischer-Tropsch derived oils, fully synthetic oils such as those based on polyethylene, polypropylene, dimer, trimer and poly butylene and the like; refinery residues or other hydrocarbon oils such as atmospheric residue, vacuum residue, fluid catalytic cracker (FCC) slurry oil, FCC cycle oil, pyrolysis gasoil, 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, asphaltene oils; used or recycled motor oils; lube oil aromatic extracts and crude oils such as heavy crude oil, distressed crude oils and similar materials that might otherwise be sent to a hydrocracker or diverted into the blending pool for a prior art high sulfur heavy (residual) marine fuel oil. Examples of Diluent Materials that are considered to be non-hydrocarbon based materials include: residual water (i.e. water that is absorbed from the humidity in the air or water that is miscible or solubilized, in some cases as microemulsions, into the hydrocarbons of the Product HMFO), fuel additives which can include, but are not limited to detergents, viscosity modifiers, pour point depressants, lubricity modifiers, de-hazers (e.g. alkoxylated phenol formaldehyde polymers), antifoaming agents (e.g. polyether modified polysiloxanes); ignition improvers; anti rust agents (e.g. succinic acid ester derivatives); 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 mixtures of these. A third group of Diluent Materials may include suspended solids or fine particulate materials that are present as a result of the handling, storage and transport of the Product HMFO or the Heavy Marine Fuel Composition, including but not limited to: carbon or hydrocarbon solids (e.g. coke, graphitic solids, or micro-agglomerated asphaltenes), iron rust and other oxidative corrosion solids, fine bulk metal particles, paint or surface coating particles, plastic or polymeric or elastomer or rubber particles (e.g. resulting from the degradation of gaskets, valve parts, etc. . . . ), catalyst fines, ceramic or mineral particles, sand, clay, and other earthen particles, bacteria and other biologically generated solids, and mixtures of these that may be present as suspended particles, but otherwise don't detract from the merchantable quality of the Heavy Marine Fuel Composition as an ISO 8217 (2017) compliant heavy (residual) marine fuel.
[0079] The blend of Product HMFO and Diluent Materials must be of merchantable quality as a low sulfur heavy (residual) marine fuel. That is the blend must be suitable for the intended use as heavy marine bunker fuel and generally be fungible as a bunker fuel for ocean going ships. Preferably the Heavy Marine Fuel Composition must retain the bulk physical properties that are required of an ISO 8217 (2017) compliant residual marine fuel oil and a sulfur content lower than the global MARPOL standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754) so that the material qualifies as MARPOL Annex VI Low Sulfur Heavy Marine Fuel Oil (LS-HMFO). As noted above, the sulfur content of the Product HMFO can be significantly lower than 0.5% wt. (i.e. below 0.1% wt sulfur (ISO 14596 or ISO 8754)) to qualify as a MARPOL Annex VI compliant Ultra-Low Sulfur Heavy Marine Fuel Oil (ULS-HMFO) and a Heavy Marine Fuel Composition likewise can be formulated to qualify as a MARPOL Annex VI compliant ULS-HMFO suitable for use as marine bunker fuel in the ECA zones. To qualify as an ISO 8217 (2017) qualified fuel, the Heavy Marine Fuel Composition of the present invention must meet those internationally accepted standards including: 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 sedimentaged (ISO 10307-2) of 0.10% wt.; a maximum carbon residuemicro 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.
[0080] Production Plant Description: Turning now to a more detailed illustrative embodiment of a production plant implementing both the core process and the oxidative desulfurizing processes disclosed herein,
[0081] It will be appreciated by one of skill in the art that additional alternative embodiments for the core process and the oxidative desulfurizing process may involve multiple vessels and reactors even though only one of each is shown. Variations using multiple vessels/reactors are contemplated by the present invention but are not illustrated in greater detail for simplicity sake. The Reactor System (11) for the core process is described in greater detail below and the use of multiple vessels for the oxidative desulfurizing process has already been described. It will be noted by one of skill in the art that in
[0082] In
[0083] As shown in
[0084] As shown in
[0085] In both
[0086] 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.
[0087] 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.
[0088] 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).
[0089] 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).
[0090] 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.
[0091] In
[0092] In
[0093] 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.
[0094] 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 (23a) 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.
[0095] Reactor System Description: The core process Reactor System (11) illustrated in
[0096] Alternative Reactor Systems in which more than one reactor vessel may be utilized in parallel or in a cascading series can easily be substituted for the single reactor vessel Reactor System 11 shown. In such an embodiment, each reactor vessel is similarly loaded with process catalyst and can be provided the heated Feed Mixture (D) via a common line. The effluent from each of the three reactors is recombined in line and forms a combined Reactor Effluent (E) for further processing as described above. The illustrated arrangement will allow the three reactors to carry out the process effectively multiplying the hydraulic capacity of the overall Reactor System. Control valves and isolation valves may also prevent feed from entering one reactor vessel but not another reactor vessel. In this way one reactor can be by-passed and placed off-line for maintenance and reloading of catalyst while the remaining reactors 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. 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.
[0097] In another illustrative embodiment cascading reactor vessels are loaded with process catalyst with the same or different activities toward metals, sulfur or other environmental contaminates to be removed. For example, one reactor may be loaded with a highly active demetaling catalyst, a second subsequent or downstream reactor may be loaded with a balanced demetaling/desulfurizing catalyst, and reactor downstream from the second reactor 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 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).
[0098] 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.
[0099] 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.
[0100] 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 NiMo, CoMo, NiW or NiCoMo 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.
[0101] 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.
[0102] 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).
[0103] 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 deep desulfurization with product sulfur levels below 0.1 ppmw.
[0104] 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.
[0105] The following example will provide one skilled in the art with a more specific illustrative embodiment for conducting the process disclosed and claimed herein:
[0106] Core Process 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 was 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 was loaded with ? hydro-demetaling catalyst and ? hydro-transition catalyst. The second reactor was loaded with all hydrodesulfurization catalyst. The catalysts in each reactor were mixed with glass beads (approximately 50% by volume) to improve liquid distribution and better control reactor temperature. For this pilot test run, we used these 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 was complete, the catalyst was activated by sulfiding the catalyst in a manner well known to one of skill in the art.
[0107] Core Process Unit Operation: Upon completion of the activating step, the pilot unit was ready to receive the feedstock HMFO and Activating Gas feed. For the present example, the Activating Gas was technical grade or better hydrogen gas. The mixed Feedstock HMFO and Activating Gas was 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).
[0108] 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 was brought to a steady state for each condition and full samples taken so analytical tests were completed. Material balance for each condition was closed before moving to the next condition.
[0109] 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%.
[0110] Process conditions in the Core Process Pilot Unit were systematically adjusted as per Table 1 to assess the impact of process conditions and optimize the performance of the process for the specific catalyst and feedstock HMFO utilized.
TABLE-US-00001 TABLE 1 Optimization of Core Process Conditions Nm.sup.3 H.sub.2/m.sup.3 Pressure HC Feed Rate oil/scf Temp (MPa(g)/ Case (ml/h), [LHSV(/h)] H.sub.2/bbl oil (? C./? F.) psig) Base 108.5 [0.25] 570/3200 372/702 13.8/2000 Baseline 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
[0111] In this way, the conditions of the core process unit will 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).
[0112] Pre-Treatment Oxidative Desulfurizing Unit Pilot Test: Approximately 1000 gm of Feedstock HMFO (3% wt sulfur) will be placed under and inert atmosphere (preferably nitrogen) and heated to approximately 100? C. (220? F.) to achieve a viscosity suitable for the pumping and flow of the HMFO as a liquid. Reported sulfur specification in heavy petroleum generally indicate that approximately 60%-75% of the sulfur content is attributable to aromatic sulfur compounds such as thiophene>>benzothiophene>>dibenzothiophene. (See for example Sulfur Speciation in Heavy Petroleums: Information from X-ray Absorption Near-Edge Structure, Geoffrey S. Waldo et al., Geochemica et Cosmochimica Acts, Vol, 55 pp 801-814) Based on this approximate speciation, 2% of the sulfur is attributable to thiophene (1.0% wt.) benezothiophene (0.5% wt.) and dibenzothiophene (0.5% wt) or a total aromatic sulfur content of about 0.183 mol equivalents in the sample. Using a molar ratio of 4:1 oxidizing agent to sulfur equivalent, cumyl hydroperoxide is used a titanium promotor poly[bis(glycerolato)(hydroxo)(cumylperoxo)titanium(IV) bisphenol A ester as those disclosed in US 8283498 (incorporated herein by reference) will be added. The oxidant, catalyst and hydrocarbons will remain in contact for a period of 15 minutes which allows the oxidation reactions of sulfur compounds in the hydrocarbon structure to occur. The mixture will then be washed with caustic, such as NaO or the ammonium chloride salt dissolved water. The wash water containing ammonium sulfide and some organic sulfur compounds will then be decanted as stream from the vessel. The HMFO stream containing catalyst and most of the sulfones, as they are more soluble in HMFO than water, will be extracted with methanol to separate the reaction by products sulfoxides and sulfones from the hydrocarbon mixture. The methanol amount used was about equal parts of the treated hydrocarbons to dissolve the oxidation by-products sulfones. About 1 W % of sulfones of total sulfones produced in the oxidation reactions will remain in the HMFO after the extraction process. The HMFO material can then be heated to about 300? C. which will result in the thermal decomposition of the remaining sulfones and the resulting HMFO product ?assed with nitrogen or other inert gas. The heated material is subsequently treated in the Core Process Pilot Test Unit described above to give a Product HMFO.
[0113] Post-Treatment Oxidative Desulfurizing Unit Pilot Test: Approximately 1000 gm of effluent from the Core Process Pilot Test Unit described above will be placed under and inert atmosphere (preferably nitrogen) and heated to approximately 100? C. (220? F.) to achieve a viscosity suitable for the pumping and flow of the HMFO as a liquid. Based on speciation of the organosulfur compounds, the hard sulfur compounds present substantially include benzothiophene and dibenzothiophene. Diluted ozone (10% by volume in nitrogen) as a gaseous oxidizing agent can be bubbled through the HFMO fluid to oxidize the residual organo-sulfur compounds. Alternatively, a kerosene peroxide (Cu hydroperoxide) generated (as disclosed in U.S. Pat. No. 2,749,284 incorporated herein by reference) and will be mixed in a ratio of one active peroxide equivalent per molar sulfur equivalent or 1.5%-2.0% wt per 1% wt. sulfur present. The mixture will be stirred for approximately 1 hour to simulate a stirred tank reactor. The HMFO containing oxidized sulfur compounds will then be subjected to extraction with methanol using approximately 800 gm methanol divided into five extraction steps. The resulting HMFO product is then fractionated with residual light hydrocarbons and other by-products being removed in a conventional manner.
[0114] Table 2 summarizes the impacts on key properties of HMFO by the Core Process Pilot Unit.
TABLE-US-00002 TABLE 2 Expected Impact of Process on Key Properties of HMFO Property Minimum Typical Maximum Sulfur Conversion/Removal 90% 95% 99% 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
[0115] Table 3 lists analytical tests to be carried out for the characterization of the Feedstock HMFO and Product HMFO. The analytical tests included 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 can understand and appreciate the effectiveness of the inventive process.
TABLE-US-00003 TABLE 3 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 compa- rable
[0116] Table 4 contains the expected analytical test results for (A) Feedstock HMFO; (B) the Core Process Product HMFO and (C) Overall Process (Core+post oxidative desulfurizing) from the inventive process. These results will indicate to one of skill in the art that the production of a ULS HMFO can be achieved. 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-00004 TABLE 4 Analytical Results A B C Sulfur Content, mass % 3.0 Less than 0.5 Less than 0.1 Density @ 15? C. 990 950 .sup.(1) 950 .sup.(1) Kinematic Viscosity @ 50? C. 380 100 .sup.(1) 100 .sup.(1) Pour Point, ? C. 20 10 10 Flash Point, ? C. 110 100 .sup.(1) 100 .sup.(1) CCAI 850 820 820 Ash Content, mass % 0.1 0.0 0.0 Total Sediment - Aged, mass % 0.1 0.0 0.0 Micro Carbon Residue, mass % 13.0 6.5 6.5 H2S, mg/kg 0 0 0 Acid Number, mg KO/g 1 0.5 0.5 Water, vol % 0.5 0 0 Specific Contaminants, mg/kg Vanadium 180 20 20 Sodium 30 1 1 Aluminum 10 1 1 Silicon 30 3 3 Calcium 15 1 1 Zinc 7 1 1 Phosphorous 2 0 0 Nickle 40 5 5 Iron 20 2 2 Distillation, ? C./? F. IBP 160/320 120/248 120/248 5% wt 235/455 225/437 225/437 10% wt 290/554 270/518 270/518 30% wt 410/770 370/698 370/698 50% wt 540/1004 470/878 470/878 70% wt 650/1202 580/1076 580/1076 90% wt 735/1355 660/1220 660/1220 FBP 820/1508 730/1346 730/1346 C:H Ratio (ASTM D3178) 1.2 1.3 1.3 SARA Analysis Saturates 16 22 22 Aromatics 50 50 50 Resins 28 25 25 Asphaltenes 6 3 3 Asphaltenes, wt % 6.0 2.5 2.5 Total Nitrogen, mg/kg 4000 3000 3000 Note: .sup.(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.
[0117] 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.