Environment-friendly marine fuel

• US 10,640,718 B2
• Filed: 10/18/2016
• Issued: 05/05/2020
• Est. Priority Date: 10/18/2016
• Status: Active Grant

• Current Assignee: Mawetal, LLC
• Original Assignee: Mawetal, LLC
• Inventors: Wohaibi, Mohammed, Pruitt, Tom F.
• Primary Examiner(s): Nguyen, Tam M
• Application Number:
  US16/089,894
• Publication Number:
  US 20190093026A1
• Time in Patent Office: 1,295 Days
• Field of Search: None
• CPC Class Codes: C10G 2300/1044 Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• CPC Class Codes: C10G 2300/1048 Middle distillates
• CPC Class Codes: C10G 2300/1074 Vacuum distillates
• CPC Class Codes: C10G 2300/1077 Vacuum residues
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/205 Metal content
• CPC Class Codes: C10G 2300/207 Acid gases, e.g. H2S, COS, SO2, HCN
• CPC Class Codes: C10G 2300/4056 Retrofitting operations
• CPC Class Codes: C10G 2300/42 Hydrogen of special source or of special composition
• CPC Class Codes: C10G 45/02 to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• CPC Class Codes: C10G 67/04 including solvent extraction as the refining step in the absence of hydrogen
• CPC Class Codes: C10G 67/14 including at least two different refining steps in the absence of hydrogen
• CPC Class Codes: C10L 1/04 essentially based on blends of hydrocarbons
• CPC Class Codes: C10L 1/08 for compression ignition
• CPC Class Codes: C10L 1/2493 compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds
• CPC Class Codes: C10L 2200/0415 Light distillates, e.g. LPG, naphtha
• CPC Class Codes: C10L 2200/0438 Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
• CPC Class Codes: C10L 2200/0446 Diesel
• CPC Class Codes: C10L 2230/22 for improving fuel economy or fuel efficiency
• CPC Class Codes: C10L 2270/026 for diesel engines, e.g. automobiles, stationary, marine
• CPC Class Codes: C10L 2270/04 : for turbines, planes, power generation
• CPC Class Codes: C10L 2270/08 : for small applications, such as tools, lamp oil, welding
• CPC Class Codes: C10L 2290/04 : Gasification
• CPC Class Codes: C10L 2290/543 : Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel
• CPC Class Codes: C10L 2290/544 : Extraction for separating fractions, components or impurities during preparation or upgrading of a fuel
• CPC Class Codes: F02M 37/22 : Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines, e.g. arrangements in the feeding system
• CPC Class Codes: H02J 2310/42 : for ships or vessels
• CPC Class Codes: Y02E 20/18 : Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]

Abstract

For the shipping industry, these fuels provide solutions to long outstanding technical problems that heretofore hindered supply of low sulfur marine fuels in quantities needed to meet worldwide sulfur reduction goals. Marine shipping use of high sulfur bunker oils is reported as largest source of world-wide transportation SOx emissions. When ships on the open seas burn cheap low grade heavy bunker oils high in sulfur, nitrogen and metals, the SOx, NOx, and metal oxides go to the environment. This invention converts essentially all of each barrel of crude feed to a single ultraclean fuel versus conventional refining where crude feed is cut into many pieces, and each piece is sent down a separate market path meeting various different product specifications. When in port, ships can use these fuels to generate and sell electricity to land based electrical grids to offset fuel cost in an environment-friendly manner.

Claims

1. A process for conversion of crude oil comprising sulfur and metals characterized in that this process separates such crude as feed into streams based on sulfur content, treats one or more liquid portions of such separate streams for sulfur removal while leaving other portions untreated, and then recombines as combination (600) a majority of the volumes of all treated and untreated liquid streams to form a liquid fuel having an actual sulfur content at or below a target sulfur content, said process comprising:

(a) separating said crude (2) by one or more distillation steps (100, 200) into fractions comprising;

(a)(1) liquid fractions at or below breakpoint (10), and

(a)(2) liquid fractions above sulfur breakpoint comprising (a)(2)(i) fractions soluble (80) in solvent used in solvent separation and (a)(2)(ii) metals containing factions comprising those fractions not soluble (90) in solvent used in solvent separation;

b) feeding to solvent separation (300) step said metals containing fractions of (a)(2) to remove metals enriched residue (90) insoluble in one or more solvents used for said solvent separation;

(c) treating, by one or more hydrotreating steps, (a)(2) liquid fractions over sulfur breakpoint which are soluble in one or more solvents used for said solvent separation (80) to form one or more hydrotreated streams (60, 70) having reduced sulfur content, and

(d) combining said hydrotreated streams (60, 70) with (a)(1) liquid fractions at or below sulfur breakpoint (10) to form said fuel (600).

2. A process in accordance with claim 1 at least one of said hydrotreated streams is an ultralow sulfur stream having 10 ppmwt or less of sulfur which is used to adjust, by reduction or addition of the amount of such stream to said combination, formation of said fuel to control actual sulfur content at or below the sulfur breakpoint as target sulfur content.

3. A process in accordance with claim 1 having only four principle unit operations of one or more of atmospheric distillation and vacuum distillation, solvent separation, and hydrotreating, and not having hydrocarbon treating operations downstream of hydrotreating except required ancillary apparatus for firing of residue, for generation of hydrogen and process utilities, for capture of metals, and sulfur and all gases comprising sulfur are directed to one or more common sulfur recovery units.

4. A process in accordance with claim 1 wherein combination fuel (600) is formed with lowest boiling portion of said untreated 1.(a)(1) liquid fractions at or below sulfur breakpoing (10) and highest boiling portion said combination fuel is treated 1.(a)(2) liquid fractions over sulfur breakpoint which are soluble (80) in one or more solvents used for said solvent separation.

5. A process in accordance with claim 1 wherein said residue is fired in one or more gasifiers for generation of electricity and at least a portion of hydrogen for said hydrotreating and for capture at least a portion of said metals in gasifier solids which are removed.

6. A process in accordance with claim 1 wherein said residue is fired in one or more boilers having flue gas sulfur and metals capture, for generation of electricity and an ancillary hydrogen generation unit operations for supply of hydrogen for said hydrotreating.

7. A process in accordance with claim 1 wherein a majority of said crude oil feed is converted to substantially one liquid fuel product wherein at least one of said hydrotreated steams is an ultralow sulfur stream having less than 10 ppmwt of sulfur, and at least one untreated fraction has a sulfur content in excess of the breakpoint and is used as trim control, by reduction or addition of the amount of such untreated fraction to said combination to adjust the sulfur content of said combination (600) to form a fuel having an actual sulfur content at or below a target sulfur content.

8. A process in accordance with claim 1 wherein said crude oil feed is converted to substantially one liquid fuel product, wherein at least one of said separate streams is a first hydrotreated reduced sulfur stream having a sulfur content less than 10 ppmwt of sulfur, and at least one of said separate streams is a second hydrotreated reduced sulfur stream having a sulfur content in the range of 0.12 to 0.18 wt. % sulfur, and said (a)(1) liquid fractions at or below breakpoint (10) is an untreated fraction having a sulfur content in excess of, at or below, the target sulfur content and either said hydrotreated stream or seond hydrotreated stream, or both, are used as trim control, by reduction or addition of the amount of such steams to said combination, to adjust the sulfur content of said combination (600) to form a fuel having an actual sulfur content at or below a target sulfur content.

9. A process in accordance with claim 1 wherein at least 70% by volume of each barrel of said crude oil feed is converted to combination (600).

10. A process in accordance with claim 1 wherein actual sulfur content of said fuel is adjusted to meet an IMO specification for marine fuel as the target sulfur content.

11. A process in accordance with claim 1 wherein a high sulfur fuel oil is added to one or more of the feeds, or is separately fed, to one or more of said distillation steps, solvent separation step or hydrotreating step.

12. A process in accordance with claim 1 for producing a fuel by combining or other co-processing a crude having the quality of untreated light tight oil or condensate, or a combination of light tight oil or condensate, with one or more untreated fractions, hydrotreated streams, or fuels produced by claim 1 wherein when flashpoint of fuel is not a consideration said light tight oil has a sulfur content in the ranges of 0.1 wt. % to 0.2 wt. % and a density, API (Deg) in the range of 38 to 57 and distillation cut fraction ranges, in weight percent of mass, of (a) 5 to 20 wt. % liquefied petroleum gas range, (b) 10 to 35 wt. % naphtha, (c) 15 to 30 wt. % kerosene, (d) 15 to 25% diesel, (e) vacuum gas oils and (f) no (0%) to 10% heavy residuals.

13. A process for integration of atmospheric and vacuum distillation, solvent separation, and hydrotreating to produce components of a fuel characterized in that the integration of this process separates feeds into streams, treats one or more portions of such separate streams, and then recombines treated and untreated streams to form a fuel having an initial boiling point being the lowest boiling point of any fraction within untreated streams combined in said fuel and highest boiling point being the highest boiling portion of effluent from solvent separation which is subsequently treated and forms a portion said fuel, said fuel having an actual sulfur content at or below a target sulfur content limit level, which process comprises

(a) feeding crude (2) comprising sulfur and metal contaminants to an atmospheric distillation column (100) and separating the feed into light overhead gases (4) and multiple cuts comprising:

(i) unstabilized wild straight run naphtha (16)

(ii) sulfur breakpoint cut (18)

(iii) light distillate over breakpoint (24)

(iv) medium distillate (26)

(v) a first heavy distillate (28)

(vi) atmospheric residual (30)

(b) feeding (a)(vi) atmospheric residual (30) to a vacuum distillation tower (200) to produce

(i) a second heavy distillate (32)

(ii) light vacuum gas oil (36)

(iii) heavy vacuum gas oil (38)

(iv) vacuum residual (50)

(c) feeding (b)(iv) vacuum residual (50) to solvent separation (300) to produce

(i) deasphalted oil (80) and

(ii) metals rich pitch (90),

(d) feeding (a)(iii) light distillate (24), (a)(iv) medium distillate (26), (a)(v) first heavy distillate (28) and (b)(i) second heavy distillate (32) to a distillate hydrotreater (430) with addition of hydrogen in presence of catalyst at hydrotreating conditions to form a stream (60) comprising

(i) wild naphtha

(ii) ultra low sulfur diesel being a reduced sulfur stream formed from combination of treated distillate steam (60) comprising (a)(iii) light distillate (24), (a)(iv) medium distillate (26), (a)(v) first heavy distillate (28) and (b)(i) second heavy distillate (32), with associated byproducts (420) comprising

(iii) sulfur containing gas stream comprising hydrogen sulfide

(iv) hydrogen rich off gas, at least a portion of which is treated for sulfur removal and is recycled as hydrogen addition (502) to either distillate hydrotreater of (d)(430) or heavy oil hydrotreater of (e) (460)

(e) feeding (b)(ii) light vacuum gas oil (36), (b)(iii) heavy vacuum gas oil (38) and (c)(i) deasphalted oil (80) to a heavy oil hydrotreater (460) with addition of hydrogen in presence of catalyst at hydrotreating conditions to form a stream (70) comprising

(i) wild naphtha

(ii) ultra low sulfur diesel being a first reduced sulfur stream formed from a first portion of the combination of treated distillate steams comprising (b)(ii) light vacuum gas oil (36), (b)(iii) heavy vacuum gas oil (38) and (c)(i) deasphalted oil (80)

(iii) a second reduced sulfur stream (70) formed from a second portion of the combination of treated distillate steams (40) comprising (b)(ii) light vacuum gas oil (36), (b)(iii) heavy vacuum gas oil (38) and (c)(i) deasphalted oil (80) with associated byproducts (420) comprising

(iv) sulfur containing gas stream comprising hydrogen sulfide

(v) hydrogen rich off gas, at least a portion of which is treated for sulfur removal and is recycled as hydrogen addition (502) to either distillate hydrotreater of (d)(430) or heavy oil hydrotreater of (e)(460), and

(f) forming said fuel product having an actual sulfur content at or below a target sulfur content limit level by combining

(i) streams without added treatment (10) of (a)(i) unstabilized wild straight run naphtha (16) and (a)(i) sulfur breakpoint cut (18) with

(ii) streams from distillate hydrotreater (60) comprising (d)(i) wild naphtha and (d)(ii) all or a portion of ultra low sulfur diesel, with

(iii) streams from heavy oil hydrotreater (70) comprising (e) (i) wild naphtha, (e)(ii) ultra low sulfur diesel and (e)(iii) a second reduced sulfur stream in a manner whereby actual sulfur content of said fuel does not exceed target sulfur content limit.

14. A process in accordance with claim 13 comprising integration of a gasification system by

(a) feeding 16.(c)(ii) pitch which is a metals rich heavy residual to one or more gasification units comprising a gasifier for partial oxidation of said stream 16.(c)(ii) in presence of steam and oxygen, to form

(i) syngas, at least a portion of which is converted to hydrogen for use in distillate hydrotreater of 16.(d) and heavy oil hydrotreater of 16.(e) and syngas for firing combustion gas turbine of a combined cycle power plant, also comprising a heat recovery generator to recover heat from gas turbine gas to produce steam which drives steam turbine, for electricity generation and

(ii) solids soot comprising a portion of metal contaminants derived from the crude feed, which solids are directed from each gasifier for metals removal, and

(b) directing all sulfur containing gas streams from said gasification and all unit operations of claim 13 to one or more gas recovery units for sulfur removal.

15. A process in accordance with claim 13 where in actual product sulfur level is achieved by adjustment by increasing or decreasing amounts to a combination of one or more of any of

(a) streams (a)(i) unstabilized wild straight run naphtha or (a)(ii) sulfur breakpoint cut, which streams have not been hydrotreated,

(b) streams to or from distillate hydrotreater, or

(c) streams to or from heavy oil hydrotreater, where adjustment is based upon measurement of relative sulfur content of each stream to the combination to form a fuel product having an actual sulfur content at or below a target sulfur content limit level.

16. A process in accordance with claim 13 achieved by

(a) feeding to the combination 16(a)(i) unstabilized wild straight run naphtha and 16.(a)(ii) sulfur breakpoint cut, each without added treatment,

(b) adjusting actual product sulfur level by increasing or decreasing amounts to the combination of one or more of any of

(i) streams to distillate hydrotreater,

(ii) streams to heavy oil hydrotreater, and

(c) then decreasing amounts, or the desulfurization severity, to the combination of one or more of any of

(i) streams from distillate hydrotreater,

(ii) streams from heavy oil hydrotreater if needed for any reason to increase the actual product sulfur level to the target sulfur level, or

(d) increasing amounts to the combination of one or more of any of

(i) streams from distillate hydrotreater,

(ii) streams from heavy oil hydrotreater if needed for any reason to decrease the actual product sulfur content at or below the target sulfur content limit level to form a fuel product having an actual sulfur content at or below a target sulfur content limit level.

17. A process in accordance with claim 13 wherein sulfur content of feed is measured by an assay which indicates end of the sulfur breakpoint cut or start of exponential rate of rise of sulfur content over run of unit volume and use such profile to control adjustments to atmospheric distillation to maximize the available amount of 16.(a)(i) unstabilized wild straight run naphtha and 16.(a)(ii) sulfur breakpoint cut which should available be without treatment and reduce the amount of streams which should be directed to hydrotreating for treatment to form a fuel product having an actual sulfur content at or below a target sulfur content limit level.

18. A process in accordance with claim 13 wherein sulfur content of feed is measured by an assay which indicates the end of the sulfur breakpoint cut or start of exponential rate of rise of sulfur content over run of unit volume and use such profile to determine and control the amount of streams to be directed to hydrotreating to form a fuel having an actual sulfur content at or below a target sulfur content limit level.

19. A process in accordance with claim 13 wherein apparatus for said atmospheric distillation, vacuum distillation, solvent separation, and hydrotreating operations are sized to have added or spare capability to process additional feeds comprising high sulfur oil or other heavy residue sourced from a different source outside the battery limits of said operations to form a fuel having an actual sulfur content at or below a target sulfur content limit level and capture at least a portion of the sulfur and metals from said additional heavy residue.

20. A process in accordance with claim 13 wherein a high sulfur fuel oil having a sulfur content greater than the target sulfur content limit level is fed to one or more of

(a) atmospheric or vacuum distillation,

(b) solvent separation,

(c) distillate hydrotreater, either separately or combined with one or more of 16.(a)(iii) light distillate, 16.(a)(iv) medium distillate, 16.(a)(v) first heavy distillate and 16 (b)(i) second heavy distillate feeds to said distillate hydrotreater, or

(d) heavy oil hydrotreater, either separately or combined with one or more of 16.(b)(i) light vacuum gas oil, 16.(b)(iii) heavy vacuum gas oil and 16.(c)(i) deasphalted oil, to form a fuel having an actual sulfur content at or below a target sulfur content limit level.

21. A process in accordance with claim 13 wherein a high sulfur fuel oil or other heavy residue from a different source of supply from than from vacuum distillation, solvent separation apparatus of claim 13, said oil or residue having a sulfur content greater than the target sulfur content limit level is fed to one or more of

(a) 16.(b) vacuum distillation tower separately or combined with 16.(a)(vi) atmospheric residual to produce at least a portion of any or all of said 16.(b)(i) a second heavy distillate, 16.(b)(ii) light vacuum gas oil, 16.(b)(iii) heavy vacuum gas oil, 16.(b)(iv) vacuum residual, or

(b) 16.(c) solvent separation separately or combined with 16.(b)(4) vacuum residual to produce 16.(c)(i) deasphalted oil and 16.(c)(ii) metals rich pitch, to form a fuel having an actual sulfur content at or below a target sulfur content limit level.

22. A process in accordance with claim 13 wherein a high sulfur fuel oil having a sulfur content less than or greater than the target sulfur content limit level is combined with one or more of

(a) streams formed from 16 (a)(i) unstabilized wild straight run naphtha and 16 (a)(ii) sulfur breakpoint cut without added treatment or

(b) streams formed from distillate hydrotreater comprising 16(d)(i) wild naphtha and 16(d)(ii) ultra low sulfur diesel, or

(c) streams formed from heavy oil hydrotreater comprising 16(e)(i) wild naphtha, 16(e)(ii) ultra low sulfur diesel and 16 (e)(iii) a second reduced sulfur stream, to form a portion of a fuel having an actual sulfur content at or below a target sulfur content limit level.

23. A process in accordance with claim 13 wherein light tight oil or condensate, or a combination of light tight oil or condensate, having low metals content and a sulfur content less than or greater the target sulfur content limit level is combined with one or more of

(a) feeds to atmospheric or vacuum distillation, solvent separation, distillate hydrotreater or heavy oil hydrotreater,

(b) streams formed from 16.(a)(i) unstabilized wild straight run naphtha and 16.(a)(ii) sulfur breakpoint cut without added treatment or

(c) streams formed from distillate hydrotreater comprising 16.(d)(i) wild naphtha and 16.(d)(ii) ultra low sulfur diesel, or

(d) streams formed from heavy oil hydrotreater comprising 16.(e)(i) wild naphtha, 16.(e)(ii) ultra low sulfur diesel and 16.(e)(iii) a second reduced sulfur stream, or

(e) a single effluent steam formed from a combination of all hydrotreated effluents of 20.(c) from distillate hydrotreater and all hydrotreated effluents of 20(d) from heavy oil hydrotreater to form a fuel having an actual sulfur content at or below a target sulfur content limit level.

24. A process in accordance with claim 13 wherein treatment for sulfur removal from sulfur containing gas streams from all unit operations where crude feed sulfur content distribution comprises (a) only relatively small portions of sulfur in basic H2S or RSH thiol type basic forms of sulfur and (b) relatively high portions of sulfur in more complex organic structure forms and treats basic less complex forms and more complex forms differently by removal by solvent and reactive chemical based treatment by more than one amine or other removal agents and solvents in one or more removal units where each ratio of removal agents in each unit is adjusted based on sulfur distribution to each unit to selectively remove less or more complex sulfur containing molecules.

25. A process in accordance with claim 13 wherein segregated steams from said distillate hydrotreater and heavy oil hydrotreater are separately directed to a shared wall separator to form common overhead gas but are separately withdrawn for subsequent combination in fuel product, trim control as part such combination or other use.