U.S. patent application number 16/511177 was filed with the patent office on 2019-11-07 for heavy fuel oil product.
The applicant listed for this patent is Duke Technologies, LLC. Invention is credited to Michael D. Ackerson, Michael Steven Byars.
Application Number | 20190338205 16/511177 |
Document ID | / |
Family ID | 68384761 |
Filed Date | 2019-11-07 |
United States Patent
Application |
20190338205 |
Kind Code |
A1 |
Ackerson; Michael D. ; et
al. |
November 7, 2019 |
Heavy Fuel Oil Product
Abstract
A heavy fuel oil product consists essentially of a
hydroprocessed product of a high-sulfur-content feedstock that is
at least one of A) a feedstock that is non-compliant with ISO 8217:
2017; B) a feedstock that is of non-merchantable quality as a
residual marine fuel oil, and C) an intermediate product obtained
by hydroprocessing a feedstock that is non-compliant with ISO 8217:
2017 so that the intermediate product is compliant with ISO 8217:
2017 but has a sulfur content of from 0.5 wt. % or more, the
hydroprocessed product having a final sulfur content (ISO 14596 or
ISO 8754) of less than 0.5 wt. %.
Inventors: |
Ackerson; Michael D.;
(Elkins, AR) ; Byars; Michael Steven;
(Fayetteville, AR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Duke Technologies, LLC |
Fayetteville |
AR |
US |
|
|
Family ID: |
68384761 |
Appl. No.: |
16/511177 |
Filed: |
July 15, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 2300/202 20130101;
C10L 2200/0446 20130101; C10G 65/14 20130101; C10L 2200/0438
20130101; C10L 1/04 20130101; C10L 2200/0469 20130101; C10G
2300/1011 20130101 |
International
Class: |
C10L 1/04 20060101
C10L001/04 |
Claims
1. A heavy fuel oil product comprising: a hydroprocessed product of
a high-sulfur-content feedstock that is at least one of A) a
feedstock that is non-compliant with ISO 8217: 2017; B) a feedstock
that is of non-merchantable quality as a residual marine fuel oil,
and C) an intermediate product obtained by hydroprocessing a
feedstock that is non-compliant with ISO 8217: 2017 so that the
intermediate product is compliant with ISO 8217: 2017 but has a
sulfur content of from 0.5 wt. % or more, the hydroprocessed
product having a final sulfur content (ISO 14596 or ISO 8754) of
less than 0.5 wt. %.
2. The product of claim 1, wherein: the high-sulfur-content
feedstock is derived from at least one of renewable and
nonrenewable feedstocks.
3. The product of claim 1, wherein: the feedstock is A.
4. The product of claim 1, wherein: the feedstock is B.
5. The product of claim 1, wherein: the feedstock is C.
6. The product of claim 1, wherein: the feedstock is A and B.
7. The product of claim 1, wherein: the hydroprocessed product has
a sulfur content (ISO 14596 or ISO 8754) of less than 0.1 wt.
%.
8. The product of claim 1, wherein: the high-sulfur-content
feedstock is A, wherein A is an intermediate product obtained by
hydroprocessing a feedstock that is compliant with ISO 8217: 2017
so that the intermediate product is non-compliant with ISO 8217:
2017.
9. The product of claim 8, wherein: the hydroprocessed product has
a sulfur content (ISO 14596 or ISO 8754) of less than 0.1 wt.
%.
10. The product of claim 9, wherein: the feedstock is C and the
hydroprocessed product has a sulfur content (ISO 14596 or ISO 8754)
of less than 0.1 wt. %.
11. The product of claim 1, wherein the feedstock is any one of A,
B, and C, wherein A, B, and C are intermediate products obtained by
hydroprocessing a feedstock that is blended with a diluent to form
a blended feedstock.
12. The product of claim 11, wherein: the diluent is non-compliant
with ISO 8217: 2017.
13. The product of claim 12, wherein: the blended feedstock is
non-compliant with ISO 8217: 2017.
14. The product of claim 12, wherein: the blended feedstock is
compliant with ISO 8217: 2017.
15. The product of claim 11, wherein: the diluent is compliant with
ISO 8217: 2017.
16. The product of claim 15, wherein: the blended feedstock is
non-compliant with ISO 8217: 2017.
17. The product of claim 15, wherein: the blended feedstock is
compliant with ISO 8217: 2017.
18. The product of claim 1, further comprising: a diluent that is
blended with the hydroprocessed product.
19. The product of claim 1, further comprising: a diluent that is
blended with the hydroprocessed product to form a blended product
that is compliant ISO 8217: 2017 and/or has a sulfur content (ISO
14596 or ISO 8754) of less than 0.1 wt. %.
20. The product of claim 19, wherein: the diluent is selected from
at least one of diesel, fuel oil, gas oil, cutter oil, renewable
oil, renewable fuel, synthetic oil, refinery residues, and lube
oils.
Description
BACKGROUND
[0001] Large ocean-going ships have relied upon heavy fuel oil
(HFO) since the 1960s. This inexpensive and widely available fuel
source provided the impetus for the rapid growth of the
international shipping industry during that time. The HFO market
has been a reliable way for refiners to utilize the viscous,
high-contaminant waste products of many crude oil refining
processes. Because of this, the HFO composition is highly variable
and can include any combination of atmospheric, vacuum, and
visbreak residues, cycle oils, slurry oil, heavy gas oils,
polycyclic aromatic hydrocarbons, reclaimed motor oils, etc., and
may be cut with a small volumes of kerosene, diesel, or other
diluents to meet the desired product specifications, particularly
for viscosity.
[0002] Because HFOs contain high levels of contaminants, and
because of the rapid growth of the international shipping industry,
emissions from ocean-going ships burning HFO are a significant
component of global air pollution. With most developed nations now
working to reduce emissions worldwide, regulations have been put in
place in a variety of industries; however the refining industry has
been an area of considerable focus.
[0003] In 1973 the MARPOL Convention was adopted at the
International Maritime Organization (IMO). The International
Convention for the Prevention of Pollution from Ships (MARPOL) is
the main international convention covering prevention of pollution
of the marine environment by ships from operational or accidental
causes. The Convention currently includes six technical Annexes.
Special Areas with strict controls on operational discharges are
included in most Annexes.
[0004] In 2005 MARPOL Annex VI set limits on SOx and NOx from ship
exhausts and prohibited deliberate emissions of ozone depleting
substances. Designated emission control areas set more stringent
standards for SOx, NOx and particulate matter. On Jan. 1, 2020, the
global limit for sulfur in fuel oil used on board ships will be
capped at 0.5% m/m (mass by mass). This is a drastic reduction from
the previous limit of 3.5% m/m. Furthermore, IMO Regulation 14 set
a maximum sulfur content of 0.1% m/m for fuel oils used inside an
Emission Control Area (ECA) after Jan. 1, 2015. As of the date of
this filing, the established ECAS include the Baltic Sea area, the
North Sea area, the North American area, and the United States
Caribbean Sea area.
[0005] These regulatory conventions have brought about an urgent
need for low sulfur (<0.5% m/m) and ultra-low sulfur (<0.1%
m/m) fuel oils for marine use. While a variety of solutions have
been proposed to meet the need for low and ultra-low sulfur fuels
(renewable fuels, fuel blending, and a switch to liquified natural
gas (LNG) or marine diesel), issues with supply, compatibility with
existing equipment, and quality of blends necessitate that
hydroprocessed fuel oils make up a larger proportion of the marine
fuel oil market for 2020 and beyond. Accordingly, improvements are
needed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] For a more complete understanding of the disclosure,
reference is now made to the following descriptions taken in
conjunction with the accompanying FIGURE, in which:
[0007] FIG. 1 is a schematic of a hydroprocessing system for
treating a high-sulfur-content feedstock showing the process flow
in accordance with particular embodiments of the invention to form
a high fuel oil product.
DETAILED DESCRIPTION
[0008] The present invention is directed to the production of a
heavy fuel oil product that meets those regulatory conventions that
are being imposed for the use of such heavy fuel oil as marine
fuels with respect to sulfur content, as well as other
requirements. This is achieved by treating a high-sulfur-content
feedstock that has certain characteristics to form a heavy fuel oil
having a low sulfur or ultra-low sulfur content. The feedstock may
be a high-sulfur-content heavy fuel oil or other material that does
not constitute a heavy fuel oil but that has a high sulfur
content.
[0009] The high-sulfur-content heavy fuel oils include those
residual-based fuel oils that are derived from process residues
from crude oil refining. These are the fractions that do not boil
or vaporize, even under vacuum conditions. Such heavy fuel or
residual-based fuel oil materials may have a high asphaltene
content that may range from 3 wt. % to 20 wt. %. Non-limiting
examples of such heavy fuel oils include atmospheric, vacuum, and
visbreak residues, cycle oils, slurry oils, heavy gas oils,
polycyclic aromatic hydrocarbons, reclaimed motor oil, etc. These
materials may be cut with small amounts (e.g., less than 20% by
volume) of cutter oil, kerosene, diesel, or other diluents to meet
the desire product specifications, particularly viscosity.
[0010] The high-sulfur-content feedstock material may be a heavy
fuel oil, as described above, with or without any diluent, or may
be a non-heavy fuel oil material. These materials may be renewable
or non-renewable materials. Non-heavy fuel oil materials may
include renewable materials or those derived from non-petroleum or
biological sources. Non-limiting examples of such renewable,
biological or non-petroleum materials are those described in U.S.
Pat. No. 9,096,804, which is incorporated herein by reference for
all purposes, including those hydroprocessing techniques described
therein.
[0011] The sulfur content (ISO 14596 or ISO 8754) of the feedstock
must be at least equal to or greater than 0.5 wt. %. In certain
embodiments, the sulfur content (ISO 14596 or ISO 8754) may be
equal to or greater than 1 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt.
%, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, and 10 wt. %. In particular
instances, the feedstock may have a sulfur content of from at
least, equal to, and/or between any two of 0.5 wt. %, 0.6 wt. %,
0.7 wt. %, 0.8 wt. %, 0.9 wt. %, 1 wt. %, 2 wt. %, 3 wt. %, 4 wt.
%, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, and 10 wt. %.
[0012] It should be noted in the description, if a numerical value
or range is presented, each numerical value should be read once as
modified by the term "about" (unless already expressly so
modified), and then read again as not so modified unless otherwise
indicated in context. Also, in the description, it should be
understood that an amount range listed or described as being
useful, suitable, or the like, is intended that any and every value
within the range, including the end points, is to be considered as
having been stated. For example, "a range of from 1 to 10" is to be
read as indicating each and every possible number along the
continuum between about 1 and about 10. Thus, even if specific
points within the range, or even no point within the range, are
explicitly identified or refer to, it is to be understood that the
inventors appreciate and understands that any and all points within
the range are to be considered to have been specified, and that
inventors possesses the entire range and all points within the
range.
[0013] In one particular embodiment, to produce the heavy fuel oil
product the high-sulfur-content feedstock that is treated is a
feedstock that is non-compliant with ISO 8217: 2017, the provisions
of which are hereby incorporated herein by reference. ISO 8217:
2017 is a regulatory standard for residual marine fuel oils with
respect to their bulk properties, but excludes the concentration
levels of environmental contaminants. Such environmental
contaminants include SO.sub.x, NO.sub.x, and particulate materials
that are produced upon combustion. Thus, in the present invention,
the feedstock used to produce the heavy fuel product may be a
feedstock that is non-compliant with ISO 8217: 2017 with respect to
its bulk properties. Such non-compliance may result from the
feedstock material characteristics failing to meet any one or more
of the bulk property characteristics set forth ISO 8217: 2017, but
excluding any environmental contaminant limits, particularly sulfur
contaminant limits.
[0014] The ISO 8217: 2017 compliant characteristics include a
maximum kinematic viscosity at 50.degree. C. (ISO 3104) between the
range from 180 mm.sup.2/s to 700 mm.sup.2/s, a maximum density at
15.degree. C. (ISO 3675) between the range of 991.0 kg/m.sup.3 to
1010.0 kg/m.sup.3, a calculated carbon aromaticity index (CCAI) of
from 780 to 870, and a flash point (ISO 2719) of no lower than
60.0.degree. C. Other characteristics of ISO 8217: 2017 include a
maximum total sediment-aged (ISO 10307-2) of 0.10 wt. %, a maximum
carbon residue--micro method (ISO 10370) between the range of 18.00
wt. % and 20.00 wt. %, and a maximum aluminum plus silicon content
(ISO10478) of 60 mg/kg.
[0015] Thus, the feedstock used for producing the HFO product may
be any high-sulfur-content feedstock, such as a heavy fuel oil
feedstock, that is outside (either below or above) any one or more
of the above-listed ranges or values or other non-listed ranges or
values with respect to ISO 8217: 2017.
[0016] In another embodiment, the HFO product is produced from a
high-sulfur-content feedstock that is of non-merchantable quality
as a residual marine fuel oil. As used herein, the expression
"non-merchantable quality as a residual marine fuel oil" is to be
construed to mean that the feedstock material does not meet the
level of quality for a residual marine fuel oil so that the fuel is
not fit for the purpose of serving as a residual fuel source for a
marine ship and cannot be commercially sold as a residual marine
fuel oil and is not fungible (or compatible) with heavy or residual
marine bunker fuel. Such feedstocks that are of a non-merchantable
quality as a residual marine fuel oil are not stable, compatible or
miscible with other residual heavy marine fuels. In certain
instances, this non-merchantable quality can be determined by using
a cleanliness test according to ASTM D4740 Static Stability Spot
Testing, which provides a rating of 1, 2, 3, 4, or 5. Those
materials that rate a 1 or 2 are considered clean and merchantable
as a residual marine fuel, while materials with a rating of 3 or
more are considered to be of unacceptable cleanness and not of
merchantable quality for use as a residual marine fuel oil. In the
present invention, the feedstock that is of a non-merchantable
quality as a residual marine fuel oil would thus have an ASTM D4740
Static Stability Spot Testing rating of 3 or more.
[0017] In still another embodiment, a heavy fuel oil product is
produced from a high-sulfur-content feedstock that constitutes an
intermediate product obtained by hydroprocessing a feedstock that
is non-compliant with ISO 8217: 2017 so that the intermediate
product is compliant with ISO 8217: 2017 but has a sulfur content
of from 0.5 wt. % or more. The intermediate product is then
hydroprocessed further so that the hydroprocessed product has a
final sulfur content (ISO 14596 or ISO 8754) of less than 0.5 wt.
%.
[0018] Any of the above-described high-sulfur-content feedstocks
may be blended with a diluent to form a blended feedstock. The
blended feedstock is then hydroprocessed to form the final heavy
fuel oil product having low or ultra-low sulfur content. The
diluents may be compliant or non-compliant with ISO 8217: 2017.
Furthermore, the blended feedstock with the added diluent may be
compliant or non-compliant with ISO 8217: 2017.
[0019] The diluents used to form the blended feedstocks from the
above-described high-sulfur-content feedstocks may include, but are
not limited to kerosene, diesel, gas oil, marine gas oil (MGO),
marine diesel oil (MDO), light liquid hydrocarbons, distillates,
vacuum gas oil (VGO), renewable oils and fuels, biodiesel,
alcohols, methanol, ethanol, synthetic hydrocarbons and oils,
Fischer-Tropsch derived hydrocarbons and oils, refinery residues,
fluid catalytic cracker (FCC) materials, FCC slurry oil, FCC cycle
oil, pyrolysis gas oil, cracked light gas oil, cracked heavy gas
oil, light cycle oil, heavy cycle oil, thermally cracked residues,
coker heavy distillate, bitumen, de-asphalted heavy oil, visbreaker
residue, slop oils, asphaltene oils, recycled motor oils, lube oil,
aromatic extracts, crude oils, previously hydroprocessed materials,
etc. With respect to previously hydroprocessed materials, these may
include a portion of the hydroprocessed product from the
high-sulfur content feedstock that is then recycled and combined
with fresh high-sulfur content to be treated.
[0020] FIG. 1 shows a schematic of a generalized system 10 to
produce a low or ultra-low sulfur heavy fuel oil product from
high-sulfur-content feedstocks. Any one or more of the
high-sulfur-content feedstocks, with or without added diluents,
described above may be used with the system 10. The system 10
includes a hydroprocessing reactor 12 formed from a reactor vessel
14 that houses the various internal components of the reactor 12,
including one or more hydroprocessing catalyst beds 16 containing a
hydroprocessing catalyst. Such hydroprocessing catalysts are well
known in the art. The configuration of the reactor and amount and
type of catalyst used in the reactor may be that that provides
sufficient conversion and removal of sulfur from the feedstock.
[0021] The reactor 12 is provided with an inlet for introducing a
feed stream 18 of the high-sulfur-content feedstock into the
interior of the reactor vessel 14. A hydrogen-containing gas 20
that is fluidly coupled to a hydrogen gas source is combined with
the feed stream and introduced into the inlet of the reactor 12.
The feedstock and hydrogen contact the hydroprocessing catalyst
where the feedstock and hydrogen react. Sulfur compounds in the
high-sulfur-content feedstock are removed from the feedstock and
converted to H.sub.2S. Nitrogen, as well as other metals, may also
be removed from the feedstock during the hydroprocessing reaction.
The reactor may be altered in configuration and in number to
accommodate the specifications required of the product, given a
specific feed. To achieve the desired product specifications, the
addition of one or more additional reactors and/or reaction zones
may be used.
[0022] Hydroprocessed reaction products 22 are removed from the
reactor 12 through an outlet. The reaction products 22 may be
cooled in a heat exchanger unit 24 and delivered to a high pressure
separator unit 26. Hydrogen and other light gases (e.g., methane,
ethane, etc.) 28 may be removed from the high pressure separator
26. If desired, removed hydrogen gas may be recycled and combined
with the hydrogen feed 20. Separated liquid products 30 from high
pressure separator may be delivered to a further separation unit
32, which may include a stripping unit. Residual gases 34, such as
H.sub.2S and other gases such as nitrogen, hydrogen, carbon
dioxide, steam, and light hydrocarbons, are removed from the
product stream 30 in the separator unit 32. Liquid byproducts 36
may also be removed. The liquid byproducts may be those
C.sub.4-C.sub.20 hydrocarbons that may be formed during the
hydroprocessing reaction.
[0023] The product stream 38 constitutes the hydroprocessed product
that forms all or a portion of the low or ultra-low sulfur heavy
fuel oil product. The heavy fuel oil product may have a final
sulfur content (ISO 14596 or ISO 8754) of less than 0.5 wt. %, 0.4
wt. %, 0.3 wt. %, 0.2 wt. %, or 0.1 wt. %. In addition to having
low or ultra-low sulfur content, the final heavy fuel oil product
may also be compliant with ISO 8217: 2017 and/or be of a
merchantable quality as a residual marine fuel oil.
[0024] In certain instances, the hydroprocessed product 38
constitutes the entire low or ultra-low sulfur heavy fuel oil
product with no diluents added. In other instances, the
hydroprocessed product may be blended with one or more diluents to
from the final low or ultra-low sulfur heavy fuel oil product. The
diluent may include but not be limited to kerosene, diesel, gas
oil, marine gas oil (MGO), marine diesel oil (MDO), light liquid
hydrocarbons, distillates, vacuum gas oil (VGO), renewable oils and
fuels, biodiesel, alcohols, methanol, ethanol, synthetic
hydrocarbons and oils, Fischer-Tropsch derived hydrocarbons and
oils, refinery residues, fluid catalytic cracker (FCC) materials,
FCC slurry oil, FCC cycle oil, pyrolysis gas oil, cracked light gas
oil, cracked heavy gas oil, light cycle oil, heavy cycle oil,
thermally cracked residues, coker heavy distillate, bitumen,
de-asphalted heavy oil, visbreaker residue, slop oils, asphaltene
oils, recycled motor oils, lube oil, aromatic extracts, crude oils,
previously hydroprocessed materials, etc.
[0025] In cases where a diluent is used to form a final blended
product that forms the final low or ultra-low sulfur heavy fuel oil
product, the diluent of the blended product may be compliant or
non-compliant with ISO 8217: 2017, while the final blended product
is compliant with ISO 8217: 2017. In other cases, the
hydroprocessed product may be non-compliant with ISO 8217: 2017 and
the diluent may be compliant or non-compliant with ISO 8217: 2017,
while the final blended product may be compliant with ISO 8217:
2017.
[0026] Additionally, the hydroprocessed product may have a sulfur
content (ISO 14596 or ISO 8754) of less than 0.5 wt. % but greater
than one of 0.4 wt. %, 0.3 wt. %, 0.2 wt. %, or 0.1 wt. %, but may
be combined with a diluent to form a blended product that forms the
final heavy fuel oil product that has a sulfur content (ISO 14596
or ISO 8754) of less than one of 0.4 wt. %, 0.3 wt. %, 0.2 wt. %,
or 0.1 wt. %.
[0027] In certain instances, the hydroprocessed product may be of
non-merchantable quality as a residual marine fuel oil, but may be
combined with a diluent to form a blended product that is of a
merchantable quality as a residual marine fuel oil.
[0028] The final heavy fuel oil product, blended or non-blended
with any diluent, may also have any one or more or all of the
characteristics of a maximum kinematic viscosity at 50.degree. C.
(ISO 3104) between the range from 180 mm.sup.2/s to 700 mm.sup.2/s,
a maximum density at 15.degree. C. (ISO 3675) between the range of
991.0 kg/m.sup.3 to 1010.0 kg/m.sup.3, a calculated carbon
aromaticity index (CCAI) of from 780 to 870, and a flash point (ISO
2719) of no lower than 60.0.degree. C., a maximum total
sediment-aged (ISO 10307-2) of 0.10 wt. %, a maximum carbon
residue--micro method (ISO 10370) between the range of 18.00 wt. %
and 20.00 wt. %, and a maximum aluminum plus silicon content
(ISO10478) of 60 mg/kg.
[0029] When combined with a diluents to form a blended product, the
hydroprocessed product may be used in an amount of at least, equal
to, and/or between any two of 75%, 7%, 77%, 78%, 79%, 80%, 81%,
82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%,
95%, 96%, 97%, 98%, 99%, and 100% by volume of the blended product.
The diluent of such blended product may be used in an amount of at
least, equal to, and/or between any two of 0% to 1%, 2%, 3%, 4%,
5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%,
19%, 20%, 21%, 22%, 23%, 24%, and 25% by volume of the blended
product.
[0030] In addition to diluents, the final heavy fuel oil product
may contain other additives and ingredients. These may include such
things as detergents, pour point depressants, viscosity or
lubricity modifiers, stabilizers, etc. These may be present in
amounts of from 5 wt. %, 4 wt. %, 3 wt. %, 2 wt. %, 1 wt. %, 0.5
wt. % or less by total weigh of the final heavy fuel oil product,
blended or non-blended with any diluent.
[0031] While the invention has been shown in only some of its
forms, it should be apparent to those skilled in the art that it is
not so limited, but is susceptible to various changes and
modifications without departing from the scope of the invention.
Accordingly, it is appropriate that the appended claims be
construed broadly and in a manner consistent with the scope of the
invention.
* * * * *