U.S. patent application number 14/141618 was filed with the patent office on 2014-07-03 for blending of dewaxed biofuels with mineral-based kero(jet) distillate cuts to provide on-spec jet fuels.
This patent application is currently assigned to EXXONMOBIL RESEARCH AND ENGINEERING COMPANY. The applicant listed for this patent is David J. Abdallah, Roger G. Gaughan, Dennis H. Hoskin, Gary James Johnston, Mike T. Noorman, Marc-Andre Poirier, Gregory P. Rockwell, Paul P. Wells. Invention is credited to David J. Abdallah, Roger G. Gaughan, Dennis H. Hoskin, Gary James Johnston, Mike T. Noorman, Marc-Andre Poirier, Gregory P. Rockwell, Paul P. Wells.
Application Number | 20140187827 14/141618 |
Document ID | / |
Family ID | 51017923 |
Filed Date | 2014-07-03 |
United States Patent
Application |
20140187827 |
Kind Code |
A1 |
Abdallah; David J. ; et
al. |
July 3, 2014 |
BLENDING OF DEWAXED BIOFUELS WITH MINERAL-BASED KERO(JET)
DISTILLATE CUTS TO PROVIDE ON-SPEC JET FUELS
Abstract
The present invention describes a method of making a jet fuel
composition comprising: providing a mineral-based kero/jet-type
distillate component having certain enumerated physico-chemical
properties, typically an off-spec jet fuel; providing a
deoxygenated and dewaxed renewable component derived from
triglycerides and/or fatty acids and having an isoparaffin to
normal paraffin ratio from about 2:1 to about 6:1 and an aromatics
content less than about 1 vol %; and blending from about 75 vol %
to about 97 vol % of the mineral-based distillate components with
from about 3 vol % to about 25 vol % of the renewable component to
form an on-spec blended jet fuel composition.
Inventors: |
Abdallah; David J.;
(Moorestown, NJ) ; Hoskin; Dennis H.; (Westampton,
NJ) ; Gaughan; Roger G.; (Sewell, NJ) ; Wells;
Paul P.; (Mullica Hill, NJ) ; Noorman; Mike T.;
(Cinnaminson, NJ) ; Johnston; Gary James;
(Chantilly, GB) ; Poirier; Marc-Andre; (Sarnia,
CA) ; Rockwell; Gregory P.; (Sarnia, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Abdallah; David J.
Hoskin; Dennis H.
Gaughan; Roger G.
Wells; Paul P.
Noorman; Mike T.
Johnston; Gary James
Poirier; Marc-Andre
Rockwell; Gregory P. |
Moorestown
Westampton
Sewell
Mullica Hill
Cinnaminson
Chantilly
Sarnia
Sarnia |
NJ
NJ
NJ
NJ
NJ |
US
US
US
US
US
GB
CA
CA |
|
|
Assignee: |
EXXONMOBIL RESEARCH AND ENGINEERING
COMPANY
Annandale
NJ
|
Family ID: |
51017923 |
Appl. No.: |
14/141618 |
Filed: |
December 27, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61746835 |
Dec 28, 2012 |
|
|
|
Current U.S.
Class: |
585/14 ;
585/319 |
Current CPC
Class: |
C10G 45/58 20130101;
C10G 3/50 20130101; C10L 1/04 20130101; C10G 3/49 20130101; C10G
2300/304 20130101; C10G 3/46 20130101; C10G 3/47 20130101; C10G
2400/08 20130101; Y02P 30/20 20151101; C10G 2300/301 20130101 |
Class at
Publication: |
585/14 ;
585/319 |
International
Class: |
C10L 1/04 20060101
C10L001/04 |
Claims
1. A method of making a jet fuel composition comprising: providing
a mineral-based kero/jet-type distillate component having an
initial boiling point of at least about 100.degree. C. and two or
more of the following enumerated properties: a T90 boiling point
from about 260.degree. C. to about 295.degree. C.; a final boiling
point from about 275.degree. C. to about 300.degree. C.; a freezing
point from about -45.degree. C. to about -20.degree. C.; a smoke
point from about 14 mm to about 19 mm; a naphthalene content from
about 2.8 vol % to about 3.5 vol %; a JFTOT VTR rating failing the
jet fuel specification; and a sulfur content from about 2000 wppm
to about 3500 wppm; providing a deoxygenated and dewaxed renewable
component derived from triglycerides and/or fatty acids and having
an isoparaffin to normal paraffin ratio from about 2:1 to about 6:1
and an aromatics content less than about 1 vol %; and blending from
about 75 vol % to about 97 vol % of the mineral-based distillate
components with from about 3 vol % to about 25 vol % of the
renewable component to form a jet fuel composition having two or
more of the following enumerated properties: a final boiling point
of at most 300.degree. C. or at least 7.degree. C. below the final
boiling point of the mineral-based distillate component alone; a
freezing point of at most -40.degree. C. or at least 4.degree. C.
less than the freezing point of the mineral-based distillate
component alone; a smoke point of at least 18 mm or at least 2 mm
more than the smoke point of the mineral-based distillate component
alone; a naphthalene content of at most 3.0 vol % or at least 0.3
vol % lower than the naphthalene content of the mineral-based
distillate component alone; a JFTOT VTR rating passing the jet fuel
specification; and a sulfur content of at most 3000 wppm or at
least 150 wppm less than the sulfur content of the mineral-based
distillate component alone.
2. The method according to claim 1, wherein the mineral-based
distillate composition has a T90 boiling point from about
270.degree. C. to about 285.degree. C. and a final boiling point
from about 285.degree. C. to about 299.degree. C.
3. The method according to claim 1, wherein the blended jet fuel
composition has all of the enumerated properties.
4. The method according to claim 1, wherein the mineral-based
distillate composition has at least five of the enumerated
properties.
5. The method according to claim 1, wherein the providing of the
renewable component comprises: providing a raw renewable
triglyceride and/or fatty acid composition having an oxygen content
and wherein at least 85% of acyl chains have from 9 to 15 carbons;
contacting the raw renewable composition with an H.sub.2-containing
gas in the presence of a deoxygenation catalyst under conditions
sufficient to achieve an oxygen content of less than 100 wppm
and/or to reduce the oxygen content by at least 98% by weight; and
simultaneously with or following the deoxygenation step, performing
dewaxing by contacting with an H.sub.2-containing gas in the
presence of a dewaxing catalyst under conditions sufficient to
predominantly cause isomerization and to cause minimal cracking,
such that the product of the dewaxing step has the requisite
isoparaffin to normal paraffin ratio and aromatics content.
6. The method according to claim 5, wherein the deoxygenation and
dewaxing steps are simultaneously performed using a single
supported metal catalyst, in which an active metal component is
disposed on a catalyst support.
7. The method according to claim 6, wherein the catalyst support
comprises a zeolitic support exhibiting a 1-dimensional 10-ring
pore structure.
8. The method according to claim 6, wherein the catalyst support
comprises zeolite beta, zeolite Y, ultrastable zeolite Y,
dealuminized zeolite Y, ZBM-30, ZSM-22, ZSM-23, ZSM-35. ZSM-48,
MCM-41, MCM-48, or a combination or intergrowth thereof.
9. The method according to claim 6 wherein the active metal
component comprises a metal from Groups 8-10 of the Periodic Table
of Elements, and optionally also comprises a metal from Group 6 of
the Periodic Table of Elements.
10. The method according to claim 9, wherein the active metal
component comprises a noble metal selected from the group
consisting of platinum, palladium, ruthenium, and combinations
thereof.
11. The method according to claim 9 wherein the active metal
component comprises at least one of cobalt, nickel, and iron, and
also comprises molybdenum and/or tungsten.
12. A blended jet fuel composition made according to the method of
claim 5.
13. A method of making a jet fuel composition comprising: providing
a mineral-based jet-type distillate component having a smoke point
of at least about 20 mm; blending from about 4 vol % to about 15
vol % of a heavy cat naphtha with from about 85 vol % to about 96
vol % of the mineral-based jet-type distillate component to form a
jet-type blend having a smoke point no more than about 18 mm;
providing a hydrotreated renewable component derived from vegetable
oil, which renewable component comprises triglycerides and/or fatty
acids and has an aromatics content less than about 1 vol %;
blending from about 8 vol % to about 15 vol % of the jet-type blend
with from about 85 vol % to about 92 vol % of the hydrotreated
vegetable oil component to form a jet fuel composition having a
smoke point of at least 19 mm and at least 0.8 mm higher than the
smoke point of the jet-type blend, as well as one or more of the
following enumerated properties: a final boiling point of at most
300.degree. C. or at least 7.degree. C. below a final boiling point
of the jet-type blend alone; a freezing point of at most
-40.degree. C. or at least 4.degree. C. less than a freezing point
of the jet-type blend alone; a naphthalene content of at most 3.0
vol % or at least 0.3 vol % lower than a naphthalene content of the
jet-type blend alone; a JFTOT VTR rating passing the jet fuel
specification; and a sulfur content of at most 3000 wppm or at
least 150 wppm less than a sulfur content of the jet-type blend
alone.
14. The method of claim 13, wherein the jet fuel composition has a
smoke point of at least about 19.5 mm.
15. The method of claim 14, further comprising the step of blending
an additional amount from about 0.5 vol % to about 3 vol % of heavy
cat naphtha with the jet fuel composition to form a modified jet
fuel composition having a smoke point between 19.0 mm and 19.2 mm,
as well as a final boiling point of at most 300.degree. C., a
freezing point of at most -40.degree. C., a naphthalene content of
at most 3.0 vol %, a JFTOT VTR rating passing the jet fuel
specification, and a sulfur content of at most 3000 wppm.
Description
CROSS-REFERENCE TO RELATE APPLICATIONS
[0001] This application claims the benefit of U.S. Application Ser.
No. 61/746,835 filed on Dec. 28, 2012; which is incorporated by
reference herein in its entirety.
FIELD OF THE INVENTION
[0002] This invention involves fit-for-purpose jet fuel
compositions and methods to for making them. In particular,
mineral-based kerosene type fuels and/or off-spec jet fuels can be
made to be on-spec by blending them with a deoxygenated and
isomerized biofuel or with a hydrotreated vegetable oil.
BACKGROUND OF THE INVENTION
[0003] Rising costs and threats of shortages and supply
interruptions have recently highlighted the need for alternative
fuel sources to mineral-based fuel products. In addition,
availability of mineral-based fuel products having expected or
desirable properties and/or product composition has been recently
changing as well. In the past, a standard solution to changing
specifications and/or fuel product availabilities was to treat
(and/or treat more severely) existing fuel compositions to result
in a fuel that could meet increasingly stringent specifications.
However, with treatment methods for existing mineral-based fuels
being expensive and/or unable to meet the volume demand, past
approaches are becoming decreasingly desirable and/or
successful.
[0004] Biofuels (renewable fuels) have particularly become a focus
for alternative fuels/fuel blends, as finding mineral-based
additives/blendstocks with the appropriate compositional and
physical properties has also been getting increasingly difficult.
There have been some publications on the subject of using renewable
feedstocks in kero(jet) applications.
[0005] U.S. Patent Application Publication No. 2009/0158637
discloses a process for producing aviation fuel from renewable
feedstocks. The feedstocks include plant oils and animal fats and
oils. The process involves treating a renewable feedstock by
hydrogenating and deoxygenating to provide n-paraffins having from
about 8 to about 24 carbon atoms. At least some of the n-paraffins
are isomerized to improve cold flow properties. At least a portion
of the paraffins are selectively cracked to provide paraffins
meeting specifications for different aviation fuels such as
JP-8.
[0006] U.S. Patent Application Publication No. 2009/0088351
discloses a method for processing triglyceride-containing,
biologically-derived oils to produce lubricants and transportation
fuels. The method comprises converting triglycerides to free fatty
acids and then separating the fatty acids by saturation type. Such
separation by type enables the preparation of both lubricants and
transportation fuels.
[0007] U.S. Patent Application Publication No. 2008/0244962
discloses a method for producing an isoparaffinic product useful as
jet fuel from a renewable feedstock. The method also includes
co-producing a jet fuel and a liquefied petroleum gas (LPG)
fraction from a renewable feedstock. The method includes
hydrotreating the renewable feedstock to produce a heavy
hydrotreated stream that includes n-paraffins and hydroisomerizing
the hydrotreating unit heavy fraction to produce a hydroisomerizing
unit heavy fraction that includes isoparaffins. The method also
includes recycling the hydroisomerizing unit heavy fraction through
the hydroisomerization unit to produce an isoparaffinic product
that may be fractionated into a jet fuel and an LPG fraction. The
produced product is a jet fuel produced from a renewable feedstock
having specified cold flow properties.
[0008] U.S. Patent Application Publication No. 2006/0229222 relates
to methods for improving the low temperature storage and
performance properties of fatty acids and their derivatives, as
well as of composition containing them, by the use of stabilizers
selected from branched chain fatty acids, cyclic fatty acids, and
polyamides. Jet fuels and diesel are mentioned as blend components
for fatty acid compositions.
[0009] U.S. Patent Application Publication No. 2008/0163542
discloses blends of petroleum based fuels with renewable fuels to
enhance the low temperature operability of the blends. Various
performance indices, such as the Cold Filter Plugging Point, the
Low Temperature Flow Test, Pour Point, and Cloud Point, are taken
as measures of the low temperature performance characteristics of
fuels such as kerosene-type aviation fuels, e.g., JP-5, JP-8, Jet
A, and Jet A-1. The bio-derived component in the blend is stated to
be no more than 50% v/v in typical cases and more typically up to
35% v/v; very low proportions down to 0.5% are mentioned but with
no advantage shown for such blends.
[0010] U.S. Patent Application Publication No. 2010/0005706
discloses fuel oil compositions based on blends of renewable and
petroleum fuels with additives to enhance the resistance to forming
particulates during low temperature storage.
[0011] Other relevant references can include U.S. Patent
Application Publication Nos. 2008/0052983, 2008/0092436,
2009/0013617, 2009/0229172, 2009/0229173. 2009/0162264,
2010/0000908, 2010/014535, 2011/0061290, 2011/0203253,
2011/0126449, and 2012/0152803; U.S. Pat. Nos. 3,573,198 and
7,928.273; PCT Publication No. WO 10/058,580; the abstract by P. H.
Steele et al., entitled "Comparison of hydroprocessed bio-oil
gasoline, diesel and jet fuel fractions characteristics to ASTM
standards for drop-in fuels", in ACS National Meeting Book of
Abstracts for the American Chemical Society Conference: 240th ACS
National Meeting and Exposition, Aug. 22-26, 2010; and the abstract
by Daniel Derr, entitled "Jet fuel from biologically-derived
triacylglycerol oils", in Preprints of Symposia--American Chemical
Society, Division of Fuel Chemistry (2010), 55(2), 414.
[0012] There are few publications and/or little publicly available
information regarding jet fuels/cuts, particularly mineral-based
kero(jet) fuels/cuts, that are off-specification in one or more
ways and possible blend components to tailor the properties of a
resulting blend to be useful as a fit-for-purpose jet fuel
composition. Highly dewaxed (isomerized) and deoxygenated
paraffinic biofuels can be particularly useful as blendstocks for
such off-specification kero(jet) fuels/cuts. Additionally or
alternately, hydrotreated vegetable oils can be particularly useful
as blendstocks for off-specification jet fuels that contain higher
concentrations of cracked components, such as low-smoke-point jet
fuels containing heavy cat naphtha.
SUMMARY OF THE INVENTION
[0013] One aspect of the invention relates to a method of making a
jet fuel composition comprising: providing a mineral-based
kero/jet-type distillate component having an initial boiling point
of at least about 100.degree. C. and two or more of the following
enumerated properties: a T90 boiling point from about 260.degree.
C. to about 295.degree. C.; a final boiling point from about
275.degree. C. to about 300.degree. C.; a freezing point from about
-50.degree. C. to about -20.degree. C.; a smoke point from about 14
mm to about 19 mm; a naphthalene content from about 2.8 vol % to
about 3.5 vol %; a JFTOT VTR rating failing the jet fuel
specification; and a sulfur content from about 2000 wppm to about
3500 wppm; providing a deoxygenated and dewaxed renewable component
derived from triglycerides and/or fatty acids and having an
isoparaffin to normal paraffin ratio from about 2:1 to about 6:1
and an aromatics content less than about 1 vol %; and blending from
about 75 vol % to about 97 vol % of the mineral-based distillate
components with from about 3 vol % to about 25 vol % of the
renewable component to form a jet fuel composition having two or
more of the following enumerated properties: a final boiling point
of at most 300.degree. C. or at least 7.degree. C. below the final
boiling point of the mineral-based distillate component alone; a
freezing point of at most -40.degree. C. or at least 4.degree. C.
less than the freezing point of the mineral-based distillate
component alone; a smoke point of at least 18 mm or at least 2 mm
more than the smoke point of the mineral-based distillate component
alone; a naphthalene content of at most 3.0 vol % or at least 0.3
vol % lower than the naphthalene content of the mineral-based
distillate component alone; a JFTOT VTR rating passing the jet fuel
specification; and a sulfur content of at most 3000 wppm or at
least 150 wppm less than the sulfur content of the mineral-based
distillate component alone.
[0014] In this aspect of the invention, the step of providing the
renewable component can comprise: providing a raw renewable
triglyceride and/or fatty acid composition having an oxygen content
and wherein at least 85% of acyl chains have from 9 to 15 carbons;
contacting the raw renewable composition with an H.sub.2-containing
gas in the presence of a dcoxygenation catalyst under conditions
sufficient to achieve an oxygen content of less than 100 wppm
and/or to reduce the oxygen content by at least 98% by weight; and
simultaneously with or following the deoxygenation step, performing
dewaxing by contacting with an H.sub.2-containing gas in the
presence of a dewaxing catalyst under conditions sufficient to
predominantly cause isomerization and to cause minimal cracking,
such that the product of the dewaxing step has the requisite
isoparaffin to normal paraffin ratio and aromatics content.
[0015] Another aspect of the invention relates to a method of
making a jet fuel composition comprising: providing a mineral-based
jet-type distillate component having a smoke point of at least
about 20 mm; blending from about 4 vol % to about 15 vol % of a
heavy cat naphtha with from about 85 vol % to about 96 vol % of the
mineral-based jet-type distillate component to form a jet-type
blend having a smoke point no more than about 18 mm; providing a
hydrotreated renewable component derived from vegetable oil, which
renewable component comprises triglycerides and/or fatty acids and
has an aromatics content less than about 1 vol %; and blending from
about 8 vol % to about 15 vol % of the jet-type blend with from
about 85 vol % to about 92 vol % of the hydrotreated vegetable oil
component to form a jet fuel composition having a smoke point of at
least 19 mm (e.g., at least about 19.5 mm) and at least 0.8 mm
higher than the smoke point of the jet-type blend, as well as one
or more (e.g., at least two, at least three, at least four, or all)
of the following enumerated properties: a final boiling point of at
most 300.degree. C. or at least 7.degree. C. below a final boiling
point of the jet-type blend alone; a freezing point of at most
-40.degree. C. or at least 4.degree. C. less than a freezing point
of the jet-type blend alone; a naphthalene content of at most 3.0
vol % or at least 0.3 vol % lower than a naphthalene content of the
jet-type blend alone; a JFTOT VTR rating passing the jet fuel
specification: and a sulfur content of at most 3000 wppm or at
least 150 wppm less than a sulfur content of the jet-type blend
alone. Optionally, where the jet fuel composition has a smoke point
of at least 19.5 mm, an additional amount from about 0.5 vol % to
about 3 vol % of heavy cat naphtha may be blended with the jet fuel
composition to form a modified jet fuel composition having a smoke
point between 19.0 mm and 19.2 mm, as well as a final boiling point
of at most 300.degree. C., a freezing point of at most -40.degree.
C., a naphthalene content of at most 3.0 vol %, a JFTOT VTR rating
passing the jet fuel specification, and a sulfur content of at most
3000 wppm.
[0016] Still another aspect of the invention relates to an on-spec
jet fuel composition made according to the method(s) described
herein/above.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 graphically shows the effect on jet-type blend smoke
point of the combination of varying proportions of heavy cat
naphtha (HCN) with jet-type distillate components.
[0018] FIG. 2 graphically shows the effect on jet fuel composition
smoke point of the combination of varying proportions of
hydrotreated vegetable oil (HVO) with jet-type blends.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0019] The present invention can involve compositions useful for
on-spec jet fuels and methods for making those compositions. Thus,
one of the methods for making a jet fuel composition according to
the invention can include: providing a mineral-based kero/jet-type
distillate component that is in some way off-specification for jet
fuel; providing a renewable component that has been treated to
achieve a set of particular compositions and/or physical/bulk
properties; and blending the components together to improve one or
more measurable properties to thus achieve a fit-for-purpose (an
on-spec) jet fuel composition.
[0020] The terms "mineral" and "mineral-based" are used herein to
denote components or compositions that are naturally occurring and
derived from non-renewable sources. Examples of such non-renewable
resources can include petroleum oil/gas deposits, shale oil/gas
deposits, natural gas deposits, coal deposits, and the like, to and
combinations thereof, including any hydrocarbon-laden deposits that
can be mined/extracted from ground/underground sources.
[0021] There are many ways in which the mineral-based kero/jet-type
distillate component according to the invention can be
characterized. One convenient way is through its physico-chemical
properties. For instance, the mineral-based kero/jet-type
distillate component can advantageously have one or more of the
following enumerated properties: an initial boiling point of at
least about 100.degree. C.; a T90 boiling point from about
260.degree. C. to about 295.degree. C.; a final boiling point from
about 275.degree. C. to about 300.degree. C.; a freezing point from
about -50.degree. C. to about -20.degree. C.; a smoke point from
about 14 mm to about 19 mm: a naphthalene content from about 2.8
vol % to about 3.5 vol %; a JFTOT VTR rating failing the jet fuel
specification; and a sulfur content from about 2000 wppm to about
3500 wppm. In some embodiments, the mineral-based kero/jet-type
distillate component can advantageously have two or more of the
enumerated properties, e.g., three or more, four or more, five or
more, six or more, or all of the enumerated properties.
[0022] When approximating boiling point ranges of compositions,
ASTM D86 can be used, although ASTM D2887 could alternately be
used. Initial boiling point can be understood to represent the
temperature at which the first material in a composition/component
is observed to turn from liquid phase to vapor phase. Conversely,
final boiling point can be understood to represent the temperature
at which the last material in a composition/component is observed
to turn from liquid phase to vapor phase. As a convention, the
temperature at which approximately "x" percent of the
composition/component has turned from liquid phase to vapor phase
can be termed the "T[x] boiling point" according to ASTM D86. Thus,
for example, the point at which .about.10% of a
composition/component has turned from liquid phase to vapor phase
is termed herein the T10 boiling point. The freezing point can be
determined according to ASTM D4529. The smoke point can be
determined according to ASTM D1322. The naphthalene content can be
determined according to ASTM D1840. The sulfur content can be
measured according to at least one of the following standard test
methods: ASTMs D1266. D2622, D4294, and D5453. JFTOT can be
determined according to ASTM D3241 using a visual tuberator (VTR),
in which passing ratings can be considered as 1, <2, 2, and
<3, and in which failing ratings can be considered as 3, <4,
4, and peacock.
[0023] Additionally or alternatively, the mineral-based
kero/jet-type distillate component can exhibit an ASTM D86 initial
boiling point of at least about 100.degree. C., e.g., at least
about 105.degree. C., at least about 110.degree. C., at least about
115.degree. C., at least about 120.degree. C., at least about
125.degree. C., at least about 130.degree. C., at least about
135.degree. C., at least about 140.degree. C., at least about
145.degree. C., at least about 150.degree. C., from about
100.degree. C. to about 160.degree. C., from about 100.degree. C.
to about 150.degree. C., from about 100.degree. C. to about
140.degree. C., from about 100.degree. C. to about 130.degree. C.,
from about 105.degree. C. to about 160.degree. C., from about
105.degree. C. to about 150.degree. C., from about 105.degree. C.
to about 140.degree. C., from about 105.degree. C. to about
130.degree. C., from about 110.degree. C. to about 160.degree. C.,
from about 110.degree. C. to about 150.degree. C., from about
110.degree. C. to about 140.degree. C., from about 110.degree. C.
to about 130.degree. C., from about 115.degree. C. to about
160.degree. C., from about 115.degree. C. to about 150.degree. C.,
from about 115.degree. C. to about 140.degree. C., from about
115.degree. C. to about 130.degree. C., from about 120.degree. C.
to about 160.degree. C. from about 120.degree. C. to about
150.degree. C., from about 120.degree. C. to about 140.degree. C.,
from about 120.degree. C. to about 130.degree. C., from about
125.degree. C. to about 160.degree. C., from about 125.degree. C.
to about 150.degree. C., or from about 125.degree. C. to about
140.degree. C. Further additionally or alternatively, the
mineral-based kero/jet-type distillate component can exhibit an
ASTM D86 10% distillation point within the range from about
150.degree. C. to about 200.degree. C., for example from about
160.degree. C. to about 180.degree. C. Still further additionally
or alternatively, the mineral-based kero/jet-type distillate
component can exhibit an ASTM D86 90% distillation point within the
range from about 250.degree. C. to about 295.degree. C., e.g., from
about 250.degree. C. to about 290.degree. C., from about
250.degree. C. to about 285.degree. C., from about 250.degree. C.
to about 280.degree. C., from about 260.degree. C. to about
295.degree. C., from about 260.degree. C. to about 290.degree. C.,
from about 260.degree. C. to about 285.degree. C., from about
260.degree. C. to about 280.degree. C., from about 270.degree. C.
to about 295.degree. C., from about 270.degree. C. to about
290.degree. C., from about 270.degree. C. to about 285.degree. C.,
or from about 270.degree. C. to about 280.degree. C. Yet further
additionally or alternatively, the mineral-based kero/jet-type
distillate component can exhibit an ASTM D86 final boiling point
less than about 300.degree. C., e.g., less than about 298.degree.
C., less than about 296.degree. C., less than about 295.degree. C.,
from about 265.degree. C. to about 300.degree. C., from about
265.degree. C. to about 295.degree. C., from about 265.degree. C.
to about 290.degree. C., from about 270.degree. C. to about
300.degree. C. from about 270.degree. C. to about 295.degree. C.,
from about 270.degree. C. to about 290.degree. C., from about
275.degree. C. to about 300.degree. C., from about 275.degree. C.
to about 295.degree. C., from about 275.degree. C. to about
290.degree. C., from about 280.degree. C. to about 300.degree. C.,
from about 280.degree. C. to about 295.degree. C., from about
280.degree. C. to about 290.degree. C., from about 285.degree. C.
to about 300.degree. C., from about 285.degree. C. to about
295.degree. C., from about 290.degree. C. to about 300.degree. C.,
or from about 295.degree. C. to about 300.degree. C.
[0024] In embodiments according to the invention, the mineral-based
kero/jct-type distillate component can exhibit a freezing point
from about -50.degree. C. to about -20.degree. C., e.g., from about
-50.degree. C. to about -25.degree. C. from about -50.degree. C. to
about -30.degree. C., from about -50.degree. C. to about
-35.degree. C. from about -50.degree. C. to about -40.degree. C.,
from about -45.degree. C. to about -25.degree. C., from about
-45.degree. C. to about -30.degree. C., from about -45.degree. C.
to about -35.degree. C., from about -45.degree. C. to about
-40.degree. C., from about -40.degree. C. to about -20.degree. C.,
from about -40.degree. C. to about -25.degree. C. from about
-40.degree. C. to about -30.degree. C., from about -35.degree. C.
to about -20.degree. C., from about -35.degree. C. to about
-25.degree. C., from about -38.degree. C. to about -20.degree. C.,
from about -38.degree. C. to about -25.degree. C., or from about
-38.degree. C. to about -30.degree. C.
[0025] In embodiments according to the invention, the mineral-based
kero/jet-type distillate component can exhibit a smoke point from
about 14 mm to about 19 mm, e.g., from about 14 mm to about 18 mm,
from about 14 mm to about 17 mm, from about 14 mm to about 16 mm,
from about 15 mm to about 19 mm from about 15 mm to about 18 mm,
from about 15 mm to about 17 mm, from about 16 mm to about 19 mm,
from about 16 mm to about 18 mm, or from about 17 mm to about 19
mm.
[0026] In embodiments according to the invention, the mineral-based
kero/jet-type distillate component can exhibit a sulfur content
from about 2000 wppm to about 3500 wppm, e.g., from about 2000 wppm
to about 3400 wppm, from about 2000 wppm to about 3300 wppm, from
about 2000 wppm to about 3200 wppm, from about 2000 wppm to about
3100 wppm, from about 2000 wppm to about 3000 wppm, from about 2000
wppm to about 2900 wppm, from about 2500 wppm to about 3500 wppm,
from about 2500 wppm to about 3400 wppm, from about 2500 wppm to
about 3300 wppm, from about 2500 wppm to about 3200 wppm, from
about 2500 wppm to about 3100 wppm, from about 2500 wppm to about
3000 wppm, from about 2500 wppm to about 2900 wppm, from about 2700
wppm to about 3500 wppm, from about 2700 wppm to about 3400 wppm,
from about 2700 wppm to about 3300 wppm, from about 2700 wppm to
about 3200 wppm, from about 2700 wppm to about 3100 wppm, from
about 2700 wppm to about 3000 wppm, from about 2700 wppm to about
2900 wppm, from about 2800 wppm to about 3500 wppm, from about 2800
wppm to about 3400 wppm, from about 2800 wppm to about 3300 wppm,
from about 2800 wppm to about 3200 wppm, from about 2800 wppm to
about 3100 wppm, from about 2800 wppm to about 3000 wppm, from
about 2800 wppm to about 2900 wppm from about 2900 wppm to about
3500 wppm, from about 2900 wppm to about 3400 wppm, from about 2900
wppm to about 3300 wppm, from about 2900 wppm to about 3200 wppm,
from about 2900 wppm to about 3100 wppm, from about 2900 wppm to
about 3000 wppm, from about 3000 wppm to about 3500 wppm, from
about 3000 wppm to about 3400 wppm, from about 3000 wppm to about
3300 wppm, from about 3000 wppm to about 3200 wppm, from about 3000
wppm to about 3100 wppm, from about 3100 wppm to about 3500 wppm,
from about 3100 wppm to about 3400 wppm, from about 3100 wppm to
about 3300 wppm, from about 3100 wppm to about 3200 wppm, from
about 3200 wppm to about 3500 wppm, from about 3200 wppm to about
3400 wppm, from about 3200 wppm to about 3300 wppm, from about 3300
wppm to about 3500 wppm, from about 3300 wppm to about 3400 wppm,
or from about 3400 wppm to about 3500 wppm.
[0027] In some embodiments, the mineral-based kero/jet-type
distillate component can optionally exhibit an olefin (unsaturated
double bond) content of at least about 0.7% by weight, e.g., at
least about 0.8% by weight, at least about 0.9% by weight, at least
about 1.0% by weight, at least about 1.1% by weight, at least about
1.2% by weight, at least about 1.3% by weight, or at least about
1.4% by weight.
[0028] Advantageously, the step of providing a renewable component
that has been treated to achieve a set of particular compositions
and/or physical/bulk properties can be satisfied by providing a
deoxygenated and dewaxed renewable component derived from
triglycerides and/or fatty acids. The deoxygenated and dewaxed
renewable component can exhibit an isoparaffin to normal paraffin
ratio from about 2:1 to about 6:1, e.g., from about 2:1 to about
5:1, from about 2:1 to about 4:1, from about 2:1 to about 3:1, from
about 3:1 to about 6:1, from about 3:1 to about 5:1, from about 3:1
to about 4:1, from about 4:1 to about 6:1 from about 4:1 to about
5:1, or from about 5:1 to about 6:1. Additionally or alternatively,
the deoxygenated and dewaxed renewable component can exhibit an
aromatics content less than about 5 vol %, e.g., less than about 4
vol %, less than about 3 vol % less than about 2 vol % less than
about 1 vol %, less than about 0.7 vol % less than about 0.5 vol %,
less than about 0.3 vol %, less than to about 0.1 vol %, or less
than about 0.05 vol %. Further additionally or alternately, the
deoxygenated and dewaxed renewable component can exhibit an olefin
(unsaturated double bond) content less than about 1.5% by weight,
e.g., less than about 1.2% by weight, less than about 1% by weight,
less than about 0.8% by weight, less than about 0.7% by weight,
less than about 0.6% by weight, less than about 0.5% by weight,
less than about 0.4% by weight, less than about 0.3% by weight,
less than about 0.2% by weight, or less than about 0.1% by
weight.
[0029] In additional or alternative embodiments, the step of
providing a renewable component that has been treated to achieve a
set of particular compositions and/or physical/bulk properties can
be satisfied by appropriately treating a raw renewable oil/fat
composition to achieve the desired characteristics.
[0030] The raw renewable oil/fat composition can advantageously be
derived predominantly (more than 50% by weight, e.g., more than 60%
by weight, more than 70% by weight, more than 80% by weight, more
than 90% by weight, more than 95% by weight, or more than 99% by
weight) or completely from triglycerides and/or fatty acid
components. Triglycerides, as used herein, can include glycerol
transesterified with three fatty acids, which are carboxylic acid
heads attached to hydrocarbon acyl tails/chains. However, in some
embodiments, triglycerides can include mono- and di-substituted
versions of glycerol, as well as tri-substituted glycerol. It
should be understood that fatty acids are described in terms of how
many carbons on their molecule, which is one more than the number
of carbons in their acyl chains (as the carboxylic acid carbon is
not counted in the acyl chain but is still part of the molecule).
Thus, a fatty acid having 14 carbons has an acyl chain with 13
carbons attached to a carboxylic acid (or ion or salt). Further,
glycerides can be defined in the same manner--where a triglyceride
has three chains of 14 carbons attached via an ester linkage to
glycerol, the triglyceride can be said to have acyl chains with 13
carbons as well as the ester carbon (which would be a carboxylic
acid, or ion or salt, carbon, if disconnected from the
glycerol).
[0031] In preferred embodiments, at least 80% of the acyl chains
(on both the triglycerides and fatty acids/ions/salts, if both are
present) can have from 7 to 17 carbons, e.g. from 7 to 15 carbons,
from 7 to 13 carbons, from 7 to 11 carbons, from 9 to 17 carbons,
from 9 to 15 carbons, from 9 to 13 carbons, or from 9 to 11
carbons. Additionally or alternatively, at least 85% of the acyl
chains can have from 7 to 17 carbons, e.g., from 7 to 15 carbons,
from 7 to 13 carbons, from 7 to 11 carbons, from 9 to 17 carbons,
from 9 to 15 carbons, from 9 to 13 carbons, or from 9 to 11
carbons. Alternatively, at least 90% of the acyl chains can have
from 7 to 17 carbons, e.g., from 7 to 15 carbons, from 7 to 13
carbons, from 7 to 11 carbons, from 9 to 17 carbons, from 9 to 15
carbons, from 9 to 13 carbons, or from 9 to 11 carbons. Further
additionally or alternatively, at least 95% of the acyl chains can
have from 7 to 17 carbons, e.g., from 7 to 15 carbons, from 7 to 13
carbons, from 7 to 11 carbons, from 9 to 17 carbons, from 9 to 15
carbons, from 9 to 13 carbons, or from 9 to 11 carbons. Still
further additionally or alternatively, at least 98% of the acyl
chains can have from 7 to 17 carbons, e.g., from 7 to 15 carbons,
from 7 to 13 carbons, from 7 to 11 carbons, from 9 to 17 carbons,
from 9 to 15 carbons, from 9 to 13 carbons, or from 9 to 11
carbons. Yet further additionally or alternatively, at least 99%
(and/or substantially all) of the acyl chains can have from 7 to 17
carbons, e.g. from 7 to 15 carbons, from 7 to 13 carbons, from 7 to
11 carbons, from 9 to 17 carbons, from 9 to 15 carbons, from 9 to
13 carbons, or from 9 to 11 carbons.
[0032] Once provided, the raw renewable fat/oil composition can be
catalytically deoxygenated and dewaxed. These steps can be done
simultaneously or in order (deoxygenation first, then dewaxing). It
should be understood that, although the steps are strictly termed
"deoxygenation" and "dewaxing" steps herein, other catalytic
reactions may take place during them. For example, it can be common
for unsaturated hydrocarbon bonds (e.g., double/olefinic bonds,
triple bonds, conjugated/aromatic bonds, etc.) to become saturated
during the deoxygenation reaction and/or during the dewaxing
reaction (e.g., due to the presence of hydrogen gas in both and the
multi-purpose catalytic capability of most deoxygenation and/or
dewaxing/isomerization catalysts).
[0033] When deoxygenation and dewaxing steps are accomplished
simultaneously, the catalytic processes may be done in a single
zone of a reactor where a deoxygenation catalyst is intimately
mixed with a dewaxing catalyst, or they may be done using a single
deoxygenation/dewaxing catalyst capable of catalyzing both
reactions.
[0034] The dewaxing catalyst can usually be the same whether used
in addition to a separate deoxygenation catalyst or as a
single/combination catalyst. Nevertheless, when separate
deoxygenation and dewaxing catalysts are used, the deoxygenation
catalyst can include any catalyst capable of catalytically
hydrotreating a hydrocarbon composition in the presence of a
H.sub.2-containing gas. Examples of such separate deoxygenation
catalysts can include, but are not necessarily limited to,
bulk/massive nickel, oxides of one or more metals of Groups 6 and
8-12 of the Periodic Table of Elements (e.g. iron, cobalt, nickel,
chromium, molybdenum, tungsten, zinc copper, and combinations
thereof), an active hydrogenation metal (e.g. selected from Groups
8-10 of the Periodic Table of Elements, such as iron, cobalt,
nickel, palladium, platinum, ruthenium, and the like, and
combinations thereof) supported on an oxide (e.g., alumina, silica,
titania, magnesia, thoria, zirconia, yttria, ceria, and
combinations thereof, including aluminosilicates,
aluminophosphates, and/or silicoaluminophosphates), and the like,
and combinations thereof. In some cases, partially (or almost
completely) spent hydrotreating catalysts (e.g., CoMo, NiMo, CoW.
NiW, CoMoW, NiMoW, etc.) can still be used to catalytically
deoxygenate. Additionally or alternately, water gas shift catalysts
(e.g., iron oxides such as Fe.sub.3O.sub.4) that would not have
enough activity for hydrotreating sulfur- and/or
nitrogen-containing feeds can be useful in catalytic deoxygenation
reactions.
[0035] In such situations where deoxygenation is done in a separate
zone and/or reactor, the deoxygenation conditions can include: an
LHSV of the input stream from about 0.1 hr.sup.-1 to about 20
hr.sup.-1, e.g., from about 0.5 hr.sup.-1 to about 1.5 hr.sup.-1 or
from about 2 hr.sup.-1 to about 20 hr.sup.-1; a weight average bed
temperature or an estimated internal temperature (WABT or EIT,
abbreviated herein as "temperature") from about 550.degree. F. to
about 700.degree. F. (about 288.degree. C. to about 371.degree.
C.), e.g., from about 575.degree. F. to about 675.degree. F. (about
302.degree. C. to about 357.degree. C.) from about 550.degree. F.
to about 625.degree. F. (about 288.degree. C. to about 329.degree.
C.), from about 550.degree. F. to about 600.degree. F. (about
288.degree. C. to about 315.degree. C.), or from about 600.degree.
F. to about 650.degree. F. (about 315.degree. C. to about
343.degree. C.); a reactor pressure from about 50 psig (about 340
kPag) to about 600 psig (about 4.1 MPag), for example from about
100 psig (about 690 kPag) to about 400 psig (about 2.8 MPag), from
about 50 psig (about 340 kPag) to about 300 psig (about 2.1 MPag),
or from about 150 psig (about 1.0 MPag) to about 350 psig (about
2.0 MPag); and a hydrogen treat gas rate from about 500 scf/bbl to
about 5000 scf/bbl (about 85 Nm.sup.3/m.sup.3 to about 850
Nm.sup.3/m.sup.3), e.g., from about 750 scf/bbl to about 3000
scf/bbl (about 130 Nm.sup.3/m.sup.3 to about 510 Nm.sup.3/m.sup.3),
from to about 750 scf/bbl to about 2500 scf/bbl (about 130
Nm.sup.3/m.sup.3 to about 470 Nm.sup.3/m.sup.3), from about 900
scf/bbl to about 2500 scf/bbl (about 150 Nm.sup.3/m.sup.3 to about
470 Nm.sup.3/m.sup.3), or from about 1000 scf/bbl to about 3000
scf/bbl (about 170 Nm.sup.3/m.sup.3 to about 510
Nm.sup.3/m.sup.3).
[0036] In a preferred embodiment, the deoxygenation step, whether
simultaneous with or initial to the dewaxing step, can be conducted
to achieve an oxygen content of less than 100 wppm (e.g., less than
75 wppm less than 50 wppm, less than 40 wppm, less than 30 wppm,
less than 25 wppm, less than 20 wppm, less than 15 wppm, less than
10 wppm, or less than 5 wppm) and/or to reduce the oxygen content
by at least 95% by weight (e.g., at least 97% by weight, at least
98% by weight, at least 99% by weight, at least 99.5% by weight, at
least 99.9% by weight, at least 99.95% by weight, or at least
99.99% by weight).
[0037] Dewaxing processes can advantageously result in
reduction/removal of longer-chain saturated hydrocarbons, which are
commonly called waxes. Dewaxing can take two forms--a hydrocracking
form, where such longer-chain saturated hydrocarbon wax molecules
are broken, or cracked, to form shorter-chain saturated
hydrocarbons that no longer exhibit the crystallization, for
example, of waxes; and an isomerization form, where longer-chain
saturated hydrocarbon wax molecules are rearranged (isomerized) to
yield roughly similarly sized hydrocarbon chains that have
hydrocarbon branches, which hydrocarbon branches thus disrupt the
crystallization that waxes would otherwise experience. In the
instant invention, it can be preferred to utilize a dewaxing
catalyst (and thus a dewaxing process) that can dewax mostly (e.g.,
as much as possible or almost completely) via isomerization
mechanisms and sparingly (e.g., as little as possible or almost not
at all) via cracking mechanisms. Particularly in such preferred
embodiments, this can enable the use of the raw renewable component
oils whose molecules exhibit relatively lower carbon numbers (lack
of cracking means smaller molecules can be used without the product
having too low a carbon number to be useful in the desired
application). In alternate embodiments, where significant dewaxing
via cracking mechanisms is catalyzed, the raw renewable component
oils containing relatively higher carbon numbers may need to be
used.
[0038] Thus, in one embodiment, the catalyst itself and/or the
catalyst support material used in the isomerization step of this
invention can have an alpha value of less than 100, e.g., less than
75, less than 60, less than 50, less than 40, less than 30, or less
than 20. The alpha value is an approximate indication of the
catalytic cracking activity of the catalyst compared to a standard
catalyst. The alpha test can give the relative rate constant (rate
of normal hexane conversion per volume of catalyst per unit time)
of the test catalyst relative to the standard catalyst which is
taken as an alpha of 1 (Rate Constant=0.016 sec.sup.-1). The alpha
test is described in U.S. Pat. No. 3,354,078 and in J. Catalysis,
4, 527 (1965); 6, 278 (1966); and 61, 395 (1980), to which
reference is made for a description of the test. The experimental
conditions of the test used to determine the alpha values referred
to in this specification include a constant temperature of
538.degree. C. and a variable flow rate as described in detail in
J. Catalysis, 61, 395 (1980).
[0039] Additionally or alternatively, the dewaxing catalyst support
materials can include zeolitic supports exhibiting a 1-dimensional
10-ring pore structure. Further additionally or alternatively, the
dewaxing catalyst support materials can include, but are not
limited to, zeolite beta, zeolite Y, ultrastable zeolite Y,
dealuminized zeolite Y, ZBM-30, ZSM-22, ZSM-23. ZSM-35. ZSM-48,
SAPO-1, SAPO-5, MeAPO-11, MeAPO-5, MCM-41, MCM-48, and combinations
and intergrowths thereof.
[0040] Catalysts useful in the dewaxing (isomerization) step
according to the invention can also contain one or more
hydrogenation metals, which can be one or more noble metals, one or
more non-noble metals, or a combination thereof. Suitable noble
metals include noble metals from Groups 8-10 of the Periodic Table
of Elements such as platinum and other members of the platinum
group, such as iridium, palladium, ruthenium, rhodium, and
combinations thereof. Suitable non-noble metals include those of
Groups 6 and 8-10 of the Periodic Table, such as chromium,
molybdenum, tungsten, cobalt, nickel, and combinations thereof
(including cobalt-molybdenum, nickel-tungsten, nickel-molybdenum,
cobalt-nickel-molybdenum, nickel-molybdenum-tungsten,
cobalt-molybdenum-tungsten, and cobalt-nickel-tungsten). The
hydrogenation metal(s) may be present in a (collective) amount from
about 0.3% to about 25%, based on the weight of the total dewaxing
catalyst composition (e.g., for noble metals, from about 0.3 wt %
to about 2.0 wt % or from about 0.5 wt % to about 1.5 wt %; for
non-noble metals, typically at least one Group 6 metal is combined
with at least one metal from Groups 8-10, such that the combination
of metals can be from about 3 wt % to about 25 wt % or from about 5
wt % to about 20 wt %).
[0041] The metal can be incorporated into the catalyst by any
suitable method or combination of methods, such as by impregnation
or ion exchange into the zeolite. The metal can be incorporated in
the form of a cationic, anionic, or neutral complex. Cationic
complexes of the type Pt(NH.sub.3).sub.4.sup.++ can be used for
exchanging metals onto the zeolite. Anionic complexes such as the
molybdate or metatungstate ions can also be useful for impregnating
metals into the catalysts.
[0042] The dcoxygenation and/or dewaxing catalyst(s), in some
embodiments, can include a binder (or matrix) material. Binder
materials, when present, can preferably comprise or be metal
oxides. Non-limiting examples of metal oxide binders can include,
but are not limited to, alumina, silica-alumina, silica-magnesia,
silica-zironcia, silica-thoria, silica-berylia, silica-titania, as
well as ternary compositions such as silica-alumina-thoria,
silica-alumina-zirconia, silica-alumina-magnesia, and
silica-magnesia-zirconia, and the like, and combinations thereof.
When binders are present, the catalyst material can be formed into
a useable shape by methods such as extrusion and/or tabletting.
[0043] The dewaxing (isomerization) reaction can be carried out in
the presence of an H.sub.2-containing gas under conditions of
elevated temperature and pressure, which, for relatively severe
isomerization in order to obtain relatively highly isomerized
renewable product, can be particularly elevated (as well as using
particular types of catalyst(s) in tandem therewith). If conducted
simultaneously with the deoxygenation step and/or if dewaxing and
deoxygenation are conducted in separate zones of a single reactor,
the conditions in the dewaxing step can be substantially the same
as in the deoxygenation step (or vice versa).
[0044] Conditions under which the isomerization process of the
present invention can be carried out can include: an LHSV of the
input stream from about 0.1 h.sup.-1 to about 20 hr.sup.-1, e.g.,
from about 0.5 hr.sup.-1 to about 1.5 hr.sup.-1 or from about 2
hr.sup.-1 to about 20 hr.sup.-1; a weight average bed temperature
or an estimated internal temperature (WABT or EIT, abbreviated
herein as "temperature") from about 600.degree. F. to about
750.degree. F. (about 315.degree. C. to about 399.degree. C.), e.g.
from about 600.degree. F. to about 700.degree. F. (about
315.degree. C. to about 371.degree. C.), from about 600.degree. F.
to about 675.degree. F. (about 315.degree. C. to about 357.degree.
C.), from about to 600.degree. F. to about 650.degree. F. (about
315.degree. C. to about 343.degree. C.), from about 625.degree. F.
to about 750.degree. F. (about 329.degree. C. to about 399.degree.
C.), from about 625.degree. F. to about 700.degree. F. (about
329.degree. C. to about 371.degree. C.), from about 625.degree. F.
to about 675.degree. F. (about 329.degree. C. to about 357.degree.
C.), from about 650.degree. F. to about 750.degree. F. (about
343.degree. C. to about 399.degree. C.), or from about 650.degree.
F. to about 700.degree. F. (about 343.degree. C. to about
371.degree. C.); a hydrogen partial pressure from 1.7 atm to 204
atm (25 psia to 3000 psia, or 170 kPaa to 20.7 MPaa), for example
6.8 atm to 170 atm (100 psia to 2500 psia, or 1.4 MPaa to 17.3
MPaa); and a hydrogen treat gas rate from about 500 scf/bbl to
about 5000 scf/bbl (about 85 Nm.sup.3/m.sup.3 to about 850
Nm.sup.3/m.sup.3), e.g., from about 750 scf/bbl to about 3000
scf/bbl (about 130 Nm.sup.3/m.sup.3 to about 510 Nm.sup.3/m.sup.3),
from about 750 scf/bbl to about 2500 scf/bbl (about 130
Nm.sup.3/m.sup.3 to about 470 Nm.sup.3/m.sup.3), from about 900
scf/bbl to about 2500 scf/bbl (about 150 Nm.sup.3/m.sup.3 to about
470 Nm.sup.3/m.sup.3), or from about 1000 scf/bbl to about 3000
scf/bbl (about 170 Nm.sup.3/m.sup.3 to about 510
Nm.sup.3/m.sup.3).
[0045] The H.sub.2-containing gas introduced into both the
deoxygenation and dewaxing (isomerization) reactors/zones can
preferably contain more than 50 vol % hydrogen. e.g., at least
about 75 vol %, at least about 80 vol %, at least about 85 vol % at
least about 90 vol %, or at least about 95 vol %.
[0046] Generally, the raw renewable oil/fat compositions/components
for deoxygenation and dewaxing can include vegetable fats/oils,
animal fats/oils, fish oils, oils/biomass extracted from
fungus/bacteria, and algae lipids/oils, as well as separated
portions of such materials. Examples of vegetable oils that can be
used in accordance with this invention include, but are not limited
to rapeseed (canola) oil, soybean oil, coconut oil, sunflower oil,
palm oil, palm kernel oil, peanut oil, linseed oil, tall oil, corn
oil, castor oil, jatropha oil, jojoba oil, olive oil, flaxseed oil,
camelina oil, safflower oil, cuphera oil, babassu oil, tallow oil,
and rice bran oil. In the processes of the present invention,
coconut, palm, palm kernel, cuphera, and babassu oils can be
preferred, particularly in circumstances where the dewaxing process
is desired to predominantly cause isomerization and to cause
minimal cracking (e.g., because their raw product contains
relatively shorter carbon number chains than many other such
oils).
[0047] Algal sources for algae oils can include, but are not
limited to, unicellular and multicellular algae. Examples of such
algae can include a rhodophyte, chlorophyte, heterokontophyte,
tribophyte, glaucophyte, chlorarachniophyte, euglenoid, haptophyte,
cryptomonad, dinoflagellum, phytoplankton, and the like, and
combinations thereof. In one embodiment, algae can be of the
classes Chlorophyceae and/or Haptophyta. Specific species can
include, but are not limited to, Neochloris oleoabundans,
Scenedesmus dimorphus, Euglena gracilis, Phaeodactylum tricornutum,
Pleurochrysis carterae, Prymnesium parvum, Tetraselmis chui, and
Chlamydomonas reinhardtii. Additional or alternate algal sources
can include one or more microalgae of the Achnanthes, Amphiprora,
Amphora, Ankistrodesmus, Asteromonas, Boekelovia, Borodinella,
Botrococcus, Bracteococcus, Chaetoceros, Carteria, Chlamydomonas,
Chlorococcum, Chlorogonium, Chlorella, Chroomonas, Chrysosphaera,
Cricosphaera, Crypthecodinium, Cryptomonas, Cyclotella, Dunaliella,
Ellipsoidon, Emiliania, Eremosphaera, Ernodesmius, Euglena,
Franceia, Fragilaria, Gloeothamnion, Haematococcus, Halocafeteria,
Hvmenomonas, Isochrvsis, Lepocinclis, Micractinium, Monoraphidium,
Nannochloris, Nannochloropsis, Navicula, Neochloris, Nephrochloris,
Nephroselmis, Nitzschia, Ochromonas, Oedogonium, Oocystis,
Ostreococcus, Pavlova, Parachlorella, Pascheria, Phaeodacylum,
Phagus, Pichochlorum, Pseudoneochloris, Pseudostaurastrum,
Platymonas, Pleurochrysis, Pleurococcus, Prototheca,
Pseudochlorella, Pyramimonas, Pyrobotrys, Scenedesmus,
Schizochlamydella, Skeletonema, Spyrogra, Stichococcus,
Tetrachlorella, Tetraselmis, Thalassiosira, Tribonema, Vaucheria,
Viridiella, and Volvox species, and/or one or more cyanobacteria of
the Agmenellum, Anabaena, Anabaenopsis, Anacvstis, Aphanizomenon,
Arthrospira, Asterocapsa, Borzia, Calothrix, Chamaesiphon,
Chlorogloeopsis, Chroococcidiopsis, Chroococcus, Crinalium,
Cyanobacterium, Cyanobium, Cyanocystis, Cyanospira, Cranothece,
Cvlindrospermopsis, Cylindrospermum, Dactylococcopsis,
Dermocarpella, Fischerella, Fremyella, Geitleria, Geitlerinema,
Gloeobacter, Gloeocapsa, Gloeothece, Halospirulina, Iyengariella,
Leptolyngbya, Limnothrix, Lyngbya, Microcoleus, Microcystis,
Myxosarcina, Nodularia, Nostoc, Nostochopsis, Oscillatoria,
Phormidium, Planktothrix, Pleurocapsa, Prochlorococcus, Prochloron,
Prochlorothrix, Pseudanabaena, Rivularia, Schizothrix, Scytonema,
Spirulina, Stanieria, Starria, Stigonema, Symploca, Synechococcus,
Synechocvstis, Tolypothrix, Trichodesmium, Tychonema, and
Xenococcus species.
[0048] In a preferred embodiment, the dewaxing step, whether
simultaneous with to or subsequent to the deoxygenation step, can
be conducted under conditions sufficient to achieve an isoparaffin
to normal paraffin ratio from about 2:1 to about 6:1 (e.g., from
about 2:1 to about 5:1, from about 2:1 to about 4:1, from about 2:1
to about 3:1, from about 3:1 to about 6:1, from about 3:1 to about
5:1, from about 3:1 to about 4:1, from about 4:1 to about 6:1 from
about 4:1 to about 5:1, or from about 5:1 to about 6:1) and/or an
aromatics content less than about 10 vol % (e.g. less than about 5
vol %, less than about 4 vol %, less than about 3 vol %, less than
about 2 vol %, less than about 1 vol %, less than about 0.5 vol %,
less than about 0.3 vol %, or less than about 0.1 vol %).
[0049] Either taking a renewable component that has been provided
to have the requisite deoxygenation and isomerization or having
conducted the requisite reactions to obtain the renewable product,
from about 3 vol % to about 25 vol % (e.g., from about 5 vol % to
about 20 vol % or from about 10 vol % to about 20 vol %) of the
renewable component/product can be blended with from about 75 vol %
to about 97 vol % (e.g. from about 80 vol % to about 95 vol % or
from about 80 vol % to about 90 vol %) of the mineral-based
distillate component to form an on-spec jet fuel composition.
[0050] The on-spec jet fuel composition can advantageously having
one or more of the following enumerated properties: a final boiling
point of at most 300.degree. C. or at least 7.degree. C. below the
final boiling point of the mineral-based distillate component
alone; a freezing point of at most -40.degree. C. or at least
4.degree. C. less than the freezing point of the mineral-based
distillate component alone; a smoke point of at least 18 mm or at
least 2 mm more than the smoke point of the mineral-based
distillate component alone; a naphthalene content of at most 3.0
vol % or at least 0.3 vol % lower than the naphthalene content of
the mineral-based distillate component alone; a JFTOT VTR rating
passing the jet fuel specification: and a sulfur content of at most
3000 wppm or at least 150 wppm less than the sulfur content of the
mineral-based distillate component alone. In some embodiments, the
on-spec jet fuel composition/blend product can advantageously have
two or more of the enumerated properties, e.g., three or more, four
or more, five or more, or all of the enumerated properties.
[0051] Another aspect of the invention relates to a method of
making a jet fuel composition comprising a first step of providing
a mineral-based jet-type distillate component having a smoke point
of at least about 19.2 mm (e.g., at least about 19.5 mm, at least
about 20 mm, at least about 20.5 mm, or at least about 21 mm;
additionally or alternatively, the smoke point can be no more than
about 26 mm, such as no more than about 25 mm, no more than about
24 mm, no more than about 23 mm, no more than about 22 mm, no more
than about 21.5 mm, no more than about 21 mm no more than about
20.5 mm, or no more than about 20 mm).
[0052] The method can comprise a second step of blending from about
2 vol % to about 20 vol % of a heavy cat naphtha (e.g., from about
2 vol % to about 18 vol %, from about 2 vol % to about 15 vol %,
from about 2 vol % to about 13 vol %, from about 2 vol % to about
12 vol %, from about 2 vol % to about 11 vol %, from about 2 vol %
to about 10 vol %, from about 2 vol % to about 9 vol %, from about
2 vol % to about 8 vol %, from about 2 vol % to about 7 vol %, from
about 2 vol % to about 6 vol %, from about 2 vol % to about 5 vol
%, from about 2 vol % to about 4 vol %, from about 4 vol % about 20
vol %, from about 4 vol % to about 18 vol %, from about 4 vol % to
about 15 vol %, from about 4 vol % to about 13 vol %, from about 4
vol % to about 12 vol %, from about 4 vol % to about 11 vol %, from
about 4 vol % to about 10 vol %, from about 4 vol % to about 9 vol
%, from about 4 vol % to about 8 vol %, from about 4 vol % to about
7 vol %, from about 4 vol % to about 6 vol %, from about 5 vol % to
about 20 vol %, from about 5 vol % to about 18 vol %, from about 5
vol % to about 15 vol %, from about 5 vol % to about 13 vol %, from
about 5 vol % to about 12 vol %, from about 5 vol % to about 11 vol
%, from about 5 vol % to about 10 vol %, from about 5 vol % to
about 9 vol %, from about 5 vol % to about 8 vol %, from about 5
vol % to about 7 vol %, from about 5 vol % to about 6 vol %, from
about 6 vol % to about 20 vol %, from about 6 vol % to about 18 vol
%, from about 6 vol % to about 15 vol %, from about 6 vol % to
about 13 vol %, from about 6 vol % to about 12 vol %, from about 6
vol % to about 11 vol %, from about 6 vol % to about 10 vol %, from
about 6 vol % to about 9 vol %, from about 6 vol % to about 8 vol
%, from about 6 vol % to about 7 vol %, from about 7 vol % to about
20 vol %, from about 7 vol % to about 18 vol %, from about 7 vol %
to about 15 vol %, from about 7 vol % to about 13 vol %, from about
7 vol % to about 12 vol %, from about 7 vol % to about 11 vol %,
from about 7 vol % to about 10 vol %, from about 7 vol % to about 9
vol %, from about 7 vol % to about 8 vol %, from about 8 vol % to
about 20 vol %, from about 8 vol % to about 18 vol %, from about 8
vol % to about 15 vol %, from about 8 vol % to about 13 vol %, from
about 8 vol % to about 12 vol %, from about 8 vol % to about 11 vol
%, from about 8 vol % to about 10 vol %, from about 8 vol % to to
about 9 vol %, from about 9 vol % to about 20 vol %, from about 9
vol % to about 18 vol %, from about 9 vol % to about 15 vol %, from
about 9 vol % to about 13 vol %, from about 9 vol % to about 12 vol
%, from about 9 vol % to about 11 vol %, from about 9 vol % to
about 10 vol %, from about 10 vol % to about 20 vol %, from about
10 vol % to about 18 vol %, from about 10 vol % to about 15 vol %,
from about 10 vol % to about 13 vol %, from about 10 vol % to about
12 vol %, from about 10 vol % to about 11 vol %, from about 11 vol
% to about 20 vol %, from about 11 vol % to about 18 vol %, from
about 11 vol % to about 15 vol %, from about 11 vol % to about 13
vol %, or from about 11 vol % to about 12 vol %) with from about 80
vol % to about 98 vol % of the mineral-based jet-type distillate
component (e.g., from about 80 vol % to about 96 vol %, from about
80 vol % to about 95 vol %, from about 80 vol % to about 94 vol %,
from about 80 vol % to about 93 vol %, from about 80 vol % to about
92 vol %, from about 80 vol % to about 91 vol %, from about 80 vol
% to about 90 vol %, from about 80 vol % to about 89 vol %, from
about 80 vol % to about 88 vol %, from about 80 vol % to about 87
vol %, from about 80 vol % to about 85 vol %, from about 80 vol %
to about 82 vol %, from about 82 vol % to about 98 vol %, from
about 82 vol % to about 96 vol %, from about 82 vol % to about 95
vol %, from about 82 vol % to about 94 vol %, from about 82 vol %
to about 93 vol %, from about 82 vol % to about 92 vol %, from
about 82 vol % to about 91 vol %, from about 82 vol % to about 90
vol %, from about 82 vol % to about 89 vol %, from about 82 vol %
to about 88 vol %, from about 82 vol % to about 87 vol %, from
about 82 vol % to about 85 vol %, from about 85 vol % to about 98
vol %, from about 85 vol % to about 96 vol %, from about 85 vol %
to about 95 vol %, from about 85 vol % to about 94 vol %, from
about 85 vol % to about 93 vol %, from about 85 vol % to about 92
vol %, from about 85 vol % to about 91 vol %, from about 85 vol %
to about 90 vol %, from about 85 vol % to about 89 vol %, from
about 85 vol % to about 88 vol %, from about 85 vol % to about 87
vol %, from about 87 vol % to about 98 vol %, from about 87 vol %
to about 96 vol %, from about 87 vol % to about 95 vol %, from
about 87 vol % to about 94 vol %, from about 87 vol % to about 93
vol %, from about 87 vol % to about 92 vol %, from about 87 vol %
to about 91 vol %, from about 87 vol % to about 90 vol %, from
about 87 vol % to about 89 vol %, from about 87 vol % to about 88
vol %, from about 88 vol % to about 98 vol %, from about 88 vol %
to about 96 vol %, from about 88 vol % to about 95 vol %, from
about 88 vol % to about 94 vol %, from about 88 vol % to to about
93 vol %, from about 88 vol % to about 92 vol %, from about 88 vol
% to about 91 vol %, from about 88 vol % to about 90 vol %, from
about 88 vol % to about 89 vol %, from about 89 vol % to about 98
vol %, from about 89 vol % to about 96 vol %, from about 89 vol %
to about 95 vol %, from about 89 vol % to about 94 vol %, from
about 89 vol % to about 93 vol %, from about 89 vol % to about 92
vol %, from about 89 vol % to about 91 vol %, from about 89 vol %
to about 90 vol %, from about 90 vol % to about 98 vol %, from
about 90 vol % to about 96 vol %, from about 90 vol % to about 95
vol %, from about 90 vol % to about 94 vol %, from about 90 vol %
to about 93 vol %, from about 90 vol % to about 92 vol %, from
about 90 vol % to about 91 vol %, from about 91 vol % to about 98
vol %, from about 91 vol % to about 96 vol %, from about 91 vol %
to about 95 vol %, from about 91 vol % to about 94 vol %, from
about 91 vol % to about 93 vol %, from about 91 vol % to about 92
vol %, from about 92 vol % to about 98 vol %, from about 92 vol %
to about 96 vol %, from about 92 vol % to about 95 vol %, from
about 92 vol % to about 94 vol %, from about 92 vol % to about 93
vol %, from about 93 vol % to about 98 vol %, from about 93 vol %
to about 96 vol %, from about 93 vol % to about 95 vol %, from
about 93 vol % to about 94 vol %, from about 94 vol % to about 98
vol %, from about 94 vol % to about 96 vol %, from about 94 vol %
to about 95 vol %, or from about 96 vol % to about 98 vol %) to
form a jet-type blend having a smoke point no more than 19.0 mm
(e.g., no more than about 18.7 mm, no more than about 18.5 mm, no
more than about 18.3 mm, no more than about 18.0 mm, no more than
about 17.7 mm, no more than about 17.5 mm, no more than about 17.3
mm, or no more than about 17.0 mm).
[0053] The method can optionally include a third step of providing
a hydrotreated renewable component derived from vegetable oil,
which renewable component typically comprises triglycerides and/or
fatty acids and has an aromatics content less than about 5 vol %
(e.g., less than about 4 vol %, less than about 3 vol %, less than
about 2 vol %, less than about 1 vol %, less than about 0.7 vol %,
less than about 0.5 vol % less than about 0.3 vol %, less than
about 0.1 vol %, or less than about 0.05 vol %).
[0054] The method can also include blending from about 5 vol % to
about 20 vol % of the jet-type blend (e.g., from about 5 vol % to
about 18 vol %, from about 5 vol % to about 15 vol %, from about 5
vol % to about 13 vol %, from about 5 vol % to about 12 vol %, from
about 5 vol % to about 11 vol %, from about 5 vol % to about 10 vol
%, from about 5 vol % to about 9 vol %, from about 5 vol % to about
8 vol %, from about 5 vol % to about 7 vol %, from about 5 vol % to
about 6 vol %, from about 6 vol % to about 20 vol %, from about 6
vol % to about 18 vol %, from about 6 vol % to about 15 vol %, from
about 6 vol % to about 13 vol %, from about 6 vol % to about 12 vol
%, from about 6 vol % to about 11 vol %, from about 6 vol % to
about 10 vol %, from about 6 vol % to about 9 vol %, from about 6
vol % to about 8 vol %, from about 6 vol % to about 7 vol %, from
about 7 vol % to about 20 vol %, from about 7 vol % to about 18 vol
%, from about 7 vol % to about 15 vol %, from about 7 vol % to
about 13 vol %, from about 7 vol % to about 12 vol %, from about 7
vol % to about 11 vol %, from about 7 vol % to about 10 vol %, from
about 7 vol % to about 9 vol %, from about 7 vol % to about 8 vol
%, from about 8 vol % to about 20 vol %, from about 8 vol % to
about 18 vol %, from about 8 vol % to about 15 vol %, from about 8
vol % to about 13 vol %, from about 8 vol % to about 12 vol %, from
about 8 vol % to about 11 vol %, from about 8 vol % to about 10 vol
%, from about 8 vol % to about 9 vol %, from about 9 vol % to about
20 vol %, from about 9 vol % to about 18 vol %, from about 9 vol %
to about 15 vol %, from about 9 vol % to about 13 vol %, from about
9 vol % to about 12 vol %, from about 9 vol % to about 11 vol %,
from about 9 vol % to about 10 vol %, from about 10 vol % to about
20 vol %, from about 10 vol % to about 18 vol %, from about 10 vol
% to about 15 vol %, from about 10 vol % to about 13 vol %, from
about 10 vol % to about 12 vol %, from about 10 vol % to about 11
vol %, from about 11 vol % to about 20 vol %, from about 11 vol %
to about 18 vol %, from about 11 vol % to about 15 vol %, from
about 11 vol % to about 13 vol %, or from about 11 vol % to about
12 vol %, from about 12 vol % to about 20 vol %, from about 12 vol
% to about 18 vol %, from about 12 vol % to about 15 vol %, from
about 12 vol % to about 13 vol %, from about 13 vol % to about 20
vol %, from about 13 vol % to about 15 vol %, or from about 15 vol
% to about 20 vol %) with from about 80 vol % to about 95 vol % of
the hydrotreated vegetable oil (e.g., from about 80 vol % to about
94 vol %, from about 80 vol % to about 93 vol %, from about 80 vol
% to about 92 vol %, from about 80 vol % to about 91 vol %, from
about 80 vol % to about 90 vol %, from about 80 vol % to about 89
vol %, from about 80 vol % to about 88 vol %, from about 80 vol %
to about 87 vol %, from about 80 vol % to about 85 vol %, from
about 80 vol % to about 82 vol %, from about 82 vol % to about 95
vol %, from about 82 vol % to about 94 vol %, from about 82 vol %
to about 93 vol %, from about 82 vol % to about 92 vol %, from
about 82 vol % to about 91 vol %, from about 82 vol % to about 90
vol %, from about 82 vol % to about 89 vol %, from about 82 vol %
to about 88 vol % from about 82 vol % to about 87 vol %, from about
82 vol % to about 85 vol %, from about 85 vol % to about 95 vol %,
from about 85 vol % to about 94 vol %, from about 85 vol % to about
93 vol %, from about 85 vol % to about 92 vol %, from about 85 vol
% to about 91 vol %, from about 85 vol % to about 90 vol %, from
about 85 vol % to about 89 vol %, from about 85 vol % to about 88
vol %, from about 85 vol % to about 87 vol %, from about 87 vol %
to about 95 vol %, from about 87 vol % to about 94 vol %, from
about 87 vol % to about 93 vol %, from about 87 vol % to about 92
vol %, from about 87 vol % to about 91 vol %, from about 87 vol %
to about 90 vol %, from about 87 vol % to about 89 vol %, from
about 87 vol % to about 88 vol %, from about 88 vol % to about 95
vol %, from about 88 vol % to about 94 vol %, from about 88 vol %
to about 93 vol %, from about 88 vol % to about 92 vol %, from
about 88 vol % to about 91 vol %, from about 88 vol % to about 90
vol %, from about 88 vol % to about 89 vol %, from about 89 vol %
to about 95 vol %, from about 89 vol % to about 94 vol %, from
about 89 vol % to about 93 vol %, from about 89 vol % to about 92
vol %, from about 89 vol % to about 91 vol %, from about 89 vol %
to about 90 vol %, from about 90 vol % to about 95 vol %, from
about 90 vol % to about 94 vol %, from about 90 vol % to about 93
vol %, from about 90 vol % to about 92 vol %, from about 90 vol %
to about 91 vol %, from about 91 vol % to about 95 vol %, from
about 91 vol % to about 94 vol %, from about 91 vol % to about 93
vol %, from about 91 vol % to about 92 vol %, from about 92 vol %
to about 95 vol %, from about 92 vol % to about 94 vol %, from
about 92 vol % to about 93 vol %, from about 93 vol % to about 95
vol %, from about 93 vol % to about 94 vol %, or from about 94 vol
% to about 95 vol %) component. This blending step can
advantageously form a jet fuel composition having a smoke point of
at least 19 mm (e.g., at least about 19.3 mm, at least about 19.5
mm, at least about 19.6 mm, at least about 19.7 mm, at least about
19.8 mm, at least about 19.9 mm, or at least about 20.0 mm;
additionally or alternatively, the smoke point can be no more than
about 26 mm, such as no more than about 25 mm, no more than about
24 mm, no more than about 23 mm, no more than about 22 mm, no more
than about 21.5 mm, no more than about 21 mm, no more than about
20.5 mm, no more than about 20 mm, or no more than about 19.8 mm)
and at to least 0.5 mm (e.g., at least 0.8 mm or at least 1.0 mm)
higher than the smoke point of the jet-type blend, as well as one
or more (e.g., at least two, at least three, at least four, or all)
of the following enumerated properties: a final boiling point of at
most 300.degree. C. or at least 7.degree. C. below a final boiling
point of the jet-type blend alone; a freezing point of at most
-40.degree. C. or at least 4.degree. C. less than a freezing point
of the jet-type blend alone; a naphthalene content of at most 3.0
vol % or at least 0.3 vol % lower than a naphthalene content of the
jet-type blend alone: a JFTOT VTR rating passing the jet fuel
specification; and a sulfur content of at most 3000 wppm or at
least 150 wppm less than a sulfur content of the jet-type blend
alone.
[0055] Optionally but preferably, where the jet fuel composition
has a smoke point of at least 19.5 mm, an additional amount from
about 0.5 vol % to about 3 vol % of heavy cat naphtha may be
blended with the jet fuel composition to form a modified jet fuel
composition having a smoke point between 19.0 mm and 19.2 mm, as
well as all of a final boiling point of at most 300.degree. C., a
freezing point of at most -40.degree. C., a naphthalene content of
at most 3.0 vol %, a JFTOT VTR rating passing the jet fuel
specification, and a sulfur content of at most 3000 wppm.
[0056] Although heavy cat naphtha (HCN) is specifically disclosed
to be used in this aspect of the invention, it should be understood
that HCN may be partially or wholly replaced with additional or
alternative components subject to a hydrocracking process.
[0057] Demand for distillate fuel components may increase in the
future, particularly relative to gasoline. In order to accommodate
this anticipated additional demand, it could be beneficial to be
able to produce distillate fuel components from feedstocks
conventionally used for gasoline production. Waxy heavy atmospheric
gas oils are one type of hydrocracking feed that could be switched
from gasoline production to distillate component production, e.g.,
for alternatively purposed usage in (modified) jet fuel
compositions such as those according to the invention.
Conventionally, waxy heavy atmospheric gas oils are often used
cracked to produce a heavy cat naphtha (HCN) that can be used in
gasoline, due to the high cloud point of the gas oil and/or to the
difficulty in achieving relatively deep desulfurization of the gas
oil. The nature of certain impurities (e.g., sulfur- and/or
nitrogen-containing molecules) in the gas oil can require
relatively severe hydrocracking/hydrotreating conditions to
mitigate. For instance, suitable feedstocks for hydrocracking
processes can include gas oils produced by the distillation of
crude oil at approximately atmospheric pressure. A crude oil
distillation tower can generally produce several grades of
atmospheric gas oils--for example, atmospheric and/or vacuum gas
oils can be used as a feedstock to a fluid catalytic cracking (FCC)
process to create an HCN component according to the invention.
[0058] Any type of reactor suitable for hydrocracking can be used
to carry out the any of the hydrocracking stages in the processes
according to the invention. Examples of such reactors can include,
but are not limited to, trickle bed, ebullating bed, moving bed,
fluidized bed, and slurry reactors.
[0059] Hydrocracking can often be interchangeably described with
catalytic dewaxing, with catalytic dewaxing usually involving both
selective cracking and hydroisomerization of the feedstock.
Hydrocracking catalysts can comprise molecular sieves such as
crystalline aluminosilicates (zeolites) or silicoaluminophosphates
(SAPOs). Additionally or alternately, the molecular sieve can be a
1-D or 3-D molecular sieve, for example a 10-member ring 1-D
molecular sieve. Examples of molecular sieves useful for
hydrocracking can include, but are not limited to, ZSM-48, ZSM-22,
ZSM-23, ZSM-35, zeolite Beta, ZSM-5, zeolite X, zeolite Y,
faujasite, ultrastable Y (USY), dealuminized Y (Deal Y), Mordenite,
ZSM-3, ZSM-4, ZSM-18, ZSM-20, and combinations thereof. Optionally,
the cracking catalyst can include a binder, such as alumina,
titania, silica, silica-alumina, zirconia, or a combination
thereof, for example alumina and/or titania, or one or more of
titania silica, and zirconia. Additionally or alternately, a
portion of the cracking catalyst can comprise or be a catalyst that
can simultaneously be used for hydrotreatment (hydrodenitrogenation
and/or hydrodesulfurization).
[0060] One feature of molecular sieves that can impact the cracking
activity of the molecular sieve includes the ratio of silica to
alumina (Si/Al.sub.2) in the molecular sieve. For instance, the
molecular sieve can have a silica to alumina ratio of about 200:1
or less, for example about 120:1 or less, about 100:1 or less,
about 90:1 or less, or about 75:1 or less. Additionally or
alternately, the molecular sieve can have a silica to alumina ratio
of at least about 30:1, for example at least about 50:1 or at least
about 65:1.
[0061] Aside from the molecular sieve component, the cracking
catalyst can also typically include a metal hydrogenation
component, such as a Group VIII metal. Suitable Group VIII metals
can include Pt, Pd, Ni, or combinations thereof. The cracking
catalyst can include at least about 0.1 wt % of the Group VIII
metal(s), for example at least about 0.3 wt %, at least about 0.5
wt %, at least about 1.0 wt %, at least about 2.5 wt %, or at least
about 5.0 wt %. Additionally or alternately, the cracking catalyst
can include about 10.0 wt % or less of the Group VIII metal(s), for
example about 5.0 wt % or less, about 2.5 wt % or less, about 1.5
wt % or less, or about 1.0 wt % or less.
[0062] In some embodiments, particularly those where hydrotreatment
and/or dewaxing activity is simultaneously desired, the cracking
catalyst can include as an additional hydrogenation component at
least one Group VIB metal, such as W and/or Mo. Such Group VIB
metals can typically be used in conjunction with the at least one
Group VIII metal, such as Ni and/or Co. An example of such an
embodiment could be a cracking catalyst that includes NiW, NiMo, or
NiMoW. When present, the dewaxing catalyst can include at least
about 0.5 wt % of the Group VIB metal(s), for example at least
about 1.0 wt %, at least about 2.5 wt %, or at least about 5.0 wt
%. Additionally or alternately, such cracking catalysts can include
about 20.0 wt % or less of the Group VIB metal(s), for example
about 15.0 wt % or less, about 10.0 wt % or less, about 5.0 wt % or
less, or about 1.0 wt % or less. Where the cracking catalyst
contains only Group VIII metals, however, Pt and/or Pd can be
preferred Group VIII metal(s).
[0063] The catalysts in any of the hydroprocessing stages according
to the processes of the invention may optionally contain additional
components, such as other transition metals (e.g., Group V metals
such as niobium), rare earth metals, organic ligands (e.g., as
added or as precursors left over from oxidation and/or
sulfidization steps), phosphorus compounds, boron compounds,
fluorine-containing compounds, silicon-containing compounds,
promoters, binders, fillers, or like agents, or combinations
thereof. The Groups referred to herein refer to Groups of the CAS
Version as found in the Periodic Table of the Elements in Hawley's
Condensed Chemical Dictionary, 13.sup.th Edition.
[0064] In certain embodiments, the hydrocracking of the feedstream
(such as a vacuum gas oil) can be accomplished to relatively
high-conversion by contacting the to feedstream with a
hydrogen-containing treat gas stream in the presence of a
hydrocracking catalyst under effective hydrocracking conditions
(e.g., sufficient to attain a conversion level of greater than 40%,
such as greater than 45%, greater than 50%, greater than 55%,
greater than 60%, or greater than 65%) so as to form a hydrocracked
product, followed by separation of the hydrocracked product into a
converted product having a boiling range maximum of about
700.degree. F. (about 371.degree. C.) and an unconverted product
having a boiling range minimum of about 700.degree. F. (about
371.degree. C.). Advantageously, the converted product can be used
for blending with a jet-type distillate component and can, in some
embodiments, exhibit a cetane number of at least 40 (for example at
least 45) and/or a sulfur content of not greater than 20 wppm (for
example, not greater than 15 wppm).
[0065] In certain embodiments, the hydrocracking conditions can be
sufficient to attain a conversion level of at least about 60%, for
example at least about 65%, at least about 70%, at least about 75%,
at least about 80% at least about 85%, or at least about 90%.
Additionally or alternatively, the hydrocracking conditions can be
sufficient to attain a conversion level of not more than about 99%,
for example not more than about 97%, not more than about 95% not
more than about 90%, not more than about 85%, not more than about
80%, or not more than about 75%. Further additionally or
alternately, the hydrocracking conditions can be sufficient to
attain a conversion level from about 55% to about 99%, for example
from about 55% to about 75% from about 60% to about 95%, or from
about 60% to about 80%. As used herein, the term "conversion
level," with reference to a feedstream being hydrocracked, means
the relative amount of change in boiling point of the individual
molecules in the feedstream from above 700.degree. F. (371.degree.
C.) to 700.degree. F. (371.degree. C.) or below. Conversion level
can be measured by any appropriate means and, for a feedstream
whose minimum boiling point is at least 700.1.degree. F.
(371.2.degree. C.), can represent the average proportion of
material that has passed through the hydrocracking process and has
a boiling point less than or equal to 700.0.degree. F.
(371.1.degree. C.), compared to the total amount of hydrocracked
material. The basic test method of determining the boiling points
or ranges of such feedstock, as well as the fuel compositions
produced according to this invention, can be by performing batch
distillation according to ASTM D86-09e1, Standard Test Method for
Distillation of Petroleum Products at Atmospheric Pressure.
[0066] Additionally or alternately, the converted hydrocracking
product can exhibit a cetane number of at least 45, for example at
least 50 or at least 51, and/or a sulfur content of not greater
than 10 wppm, for example not greater than about 8 wppm, not
greater than about 7 wppm, not greater than about 6 wppm, or not
greater than about 5 wppm. Cetane number can be measured according
to any appropriate measurement, e.g., ASTM D 613.
[0067] In an embodiment, the effective hydrocracking conditions can
comprise one or more of: a weight average bed temperature (WABT)
from about 550.degree. F. (about 288.degree. C.) to about
800.degree. F. (about 427.degree. C.); a total pressure from about
300 psig (about 2.1 MPag) to about 3000 psig (about 20.7 MPag), for
example from about 700 psig (about 4.8 MPag) to about 2000 psig
(about 13.8 MPag); an LHSV from about 0.1 hr.sup.-1 to about 20
hr.sup.-1, for example from about 0.2 hr.sup.-1 to about 10
hr.sup.-1; and a hydrogen treat gas rate from about 500 scf/bbl
(about 85 Nm.sup.3/m.sup.3) to about 10000 scf/bbl (about 1700
Nm.sup.3/m.sup.3), for example from about 750 scf/bbl (about 130
Nm.sup.3/m.sup.3) to about 7000 scf/bbl (about 1200
Nm.sup.3/m.sup.3) or from about 1000 scf/bbl (about 170
Nm.sup.3/m.sup.3) to about 5000 scf/bbl (about 850
Nm.sup.3/m.sup.3).
[0068] Treat gas, as referred to herein, can be either pure
hydrogen or a hydrogen-containing gas, which contains hydrogen in
an amount at least sufficient for the intended reaction purpose(s),
optionally in addition to one or more other gases (e.g., nitrogen,
light hydrocarbons such as methane, and the like, and combinations
thereof) that generally do not adversely interfere with or affect
either the reactions or the products. Impurities, such as H.sub.2S
and NH.sub.3, are typically undesirable and would typically be
removed from, or reduced to desirably low levels in, the treat gas
before it is conducted to the reactor stage(s). The treat gas
stream introduced into a reaction stage can preferably contain at
least about 50 vol %, for example at least about 75 vol %,
hydrogen.
[0069] Advantageously, the distillate yield from the hydrocracking
step can be desirably relatively high. For instance, the converted
hydrocracking product can have a yield of material boiling in the
range between 350.degree. F. (177.degree. C.) and 700.degree. F.
(371.degree. C.) of at least 40 wt %, for example at least 45 wt %,
at least 50 wt %, at least 55 wt %, at least 60 wt %, at least 65
wt %, or at least 70 wt %, based on the weight of the entire
hydrocracking feedstock.
[0070] Additionally or alternately, the present invention can
include one or more of the following embodiments.
Embodiment 1
[0071] A method of making a jet fuel composition comprising:
providing a mineral-based kero/jet-type distillate component having
an initial boiling point of at least about 100.degree. C. and two
or more of the following enumerated properties: a T90 boiling point
from about 260.degree. C. to about 295.degree. C.; a final boiling
point from about 275.degree. C. to about 300.degree. C.; a freezing
point from about -45.degree. C. to about -20.degree. C.; a smoke
point from about 14 mm to about 19 mm; a naphthalene content from
about 2.8 vol % to about 3.5 vol %; a JFTOT VTR rating failing the
jet fuel specification; and a sulfur content from about 2000 wppm
to about 3500 wppm; providing a deoxygenated and dewaxed renewable
component derived from triglycerides and/or fatty acids and having
an isoparaffin to normal paraffin ratio from about 2:1 to about 6:1
and an aromatics content less than about 1 vol %; and blending from
about 75 vol % to about 97 vol % of the mineral-based distillate
components with from about 3 vol % to about 25 vol % of the
renewable component to form a jet fuel composition having two or
more of the following enumerated properties: a final boiling point
of at most 300.degree. C. or at least 7.degree. C. below the final
boiling point of the mineral-based distillate component alone; a
freezing point of at most -40.degree. C. or at least 4.degree. C.
less than the freezing point of the mineral-based distillate
component alone; a smoke point of at least 18 mm or at least 2 mm
more than the smoke point of the mineral-based distillate component
alone; a naphthalene content of at most 3.0 vol % or at least 0.3
vol % lower than the naphthalene content of the mineral-based
distillate component alone; a JFTOT VTR rating passing the jet fuel
specification; and a sulfur content of at most 3000 wppm or at
least 150 wppm less than the sulfur content of the mineral-based
distillate component alone.
Embodiment 2
[0072] The method according to embodiment 1, wherein the
mineral-based distillate composition has a T90 boiling point from
about 270.degree. C. to about 285.degree. C. and a final boiling
point from about 285.degree. C. to about 299.degree. C.
Embodiment 3
[0073] The method according to embodiment 1 or embodiment 2,
wherein the blended jet fuel composition has all of the enumerated
properties.
Embodiment 4
[0074] The method according to any one of the previous embodiments,
wherein the mineral-based distillate composition has at least five
of the to enumerated properties.
Embodiment 5
[0075] The method according to claim 1, wherein the providing of
the renewable component comprises: providing a raw renewable
triglyceride and/or fatty acid composition having an oxygen content
and wherein at least 85% of acyl chains have from 9 to 15 carbons;
contacting the raw renewable composition with an H.sub.2-containing
gas in the presence of a deoxygenation catalyst under conditions
sufficient to achieve an oxygen content of less than 100 wppm
and/or to reduce the oxygen content by at least 98% by weight; and
simultaneously with or following the deoxygenation step, performing
dewaxing by contacting with an H.sub.2-containing gas in the
presence of a dewaxing catalyst under conditions sufficient to
predominantly cause isomerization and to cause minimal cracking,
such that the product of the dewaxing step has the requisite
isoparaffin to normal paraffin ratio and aromatics content.
Embodiment 6
[0076] The method according to embodiment 5, wherein the
deoxygenation and dewaxing steps are simultaneously performed using
a single supported metal catalyst, in which an active metal
component is disposed on a catalyst support.
Embodiment 7
[0077] The method according to embodiment 6, wherein the catalyst
support comprises a zeolitic support exhibiting a 1-dimensional
10-ring pore structure.
Embodiment 8
[0078] The method according to embodiment 6 or embodiment 7,
wherein the catalyst support comprises zeolite beta, zeolite Y,
ultrastable zeolite Y, dealuminized zeolite Y, ZBM-30, ZSM-22,
ZSM-23, ZSM-35, ZSM-48, MCM-41, MCM-48, or a combination or
intergrowth thereof.
Embodiment 9
[0079] The method according to any one of embodiments 6-8, wherein
the active metal component comprises a metal from Groups 8-10 of
the Periodic Table of Elements, and optionally also comprises a
metal from Group 6 of the Periodic Table of Elements.
Embodiment 10
[0080] The method according to embodiment 9, wherein the active
metal component comprises a noble metal selected from the group
consisting of platinum, palladium, ruthenium, and combinations
thereof.
Embodiment 11
[0081] The method according to embodiment 9, wherein the active
metal component comprises at least one of cobalt, nickel, and iron,
and also to comprises molybdenum and/or tungsten.
Embodiment 12
[0082] A method of making a jet fuel composition comprising:
providing a mineral-based jet-type distillate component having a
smoke point of at least about 19.2 mm (e.g., at least about 19.5
mm, at least about 20 mm, at least about 20.5 mm, or at least about
21 mm; additionally or alternatively, the smoke point can be no
more than about 26 mm, such as no more than about 25 mm, no more
than about 24 mm, no more than about 23 mm, no more than about 22
mm, no more than about 21.5 mm, no more than about 21 mm, no more
than about 20.5 mm, or no more than about 20 mm); blending from
about 2 vol % to about 20 vol % of a heavy cat naphtha (e.g., from
about 2 vol % to about 18 vol %, from about 2 vol % to about 15 vol
%, from about 2 vol % to about 13 vol %, from about 2 vol % to
about 12 vol %, from about 2 vol % to about 11 vol %, from about 2
vol % to about 10 vol %, from about 2 vol % to about 9 vol %, from
about 2 vol % to about 8 vol %, from about 2 vol % to about 7 vol
%, from about 2 vol % to about 6 vol %, from about 2 vol % to about
5 vol %, from about 2 vol % to about 4 vol %, from about 4 vol % to
about 20 vol %, from about 4 vol % to about 18 vol %, from about 4
vol % to about 15 vol %, from about 4 vol % to about 13 vol %, from
about 4 vol % to about 12 vol %, from about 4 vol % to about 11 vol
%, from about 4 vol % to about 10 vol %, from about 4 vol % to
about 9 vol %, from about 4 vol % to about 8 vol %, from about 4
vol % to about 7 vol %, from about 4 vol % to about 6 vol %, from
about 5 vol % to about 20 vol %, from about 5 vol % to about 18 vol
%, from about 5 vol % to about 15 vol %, from about 5 vol % to
about 13 vol %, from about 5 vol % to about 12 vol %, from about 5
vol % to about 11 vol %, from about 5 vol % to about 10 vol %, from
about 5 vol % to about 9 vol %, from about 5 vol % to about 8 vol
%, from about 5 vol % to about 7 vol %, from about 5 vol % to about
6 vol %, from about 6 vol % to about 20 vol %, from about 6 vol %
to about 18 vol %, from about 6 vol % to about 15 vol %, from about
6 vol % to about 13 vol %, from about 6 vol % to about 12 vol %,
from about 6 vol % to about 11 vol %, from about 6 vol % to about
10 vol %, from about 6 vol % to about 9 vol %, from about 6 vol %
to about 8 vol %, from about 6 vol % to about 7 vol %, from about 7
vol % to about 20 vol %, from about 7 vol % to about 18 vol %, from
about 7 vol % to about 15 vol %, from about 7 vol % to about 13 vol
%, from about 7 vol % to about 12 vol %, from about 7 vol % to
about 11 vol %, from about 7 vol % to about 10 vol %, from about 7
vol % to about 9 vol %, from about 7 vol % to about 8 to vol %,
from about 8 vol % to about 20 vol %, from about 8 vol % to about
18 vol %, from about 8 vol % to about 15 vol %, from about 8 vol %
to about 13 vol %, from about 8 vol % to about 12 vol %, from about
8 vol % to about 11 vol %, from about 8 vol % to about 10 vol %,
from about 8 vol % to about 9 vol %, from about 9 vol % to about 20
vol %, from about 9 vol % to about 18 vol %, from about 9 vol % to
about 15 vol %, from about 9 vol % to about 13 vol %, from about 9
vol % to about 12 vol %, from about 9 vol % to about 11 vol %, from
about 9 vol % to about 10 vol %, from about 10 vol % to about 20
vol %, from about 10 vol % to about 18 vol %, from about 10 vol %
to about 15 vol %, from about 10 vol % to about 13 vol %, from
about 10 vol % to about 12 vol %, from about 10 vol % to about 11
vol %, from about 11 vol % to about 20 vol %, from about 11 vol %
to about 18 vol %, from about 11 vol % to about 15 vol %, from
about 11 vol % to about 13 vol %, or from about 11 vol % to about
12 vol %) with from about 80 vol % to about 98 vol % of the
mineral-based jet-type distillate component (e.g. from about 80 vol
% to about 96 vol %, from about 80 vol % to about 95 vol %, from
about 80 vol % to about 94 vol %, from about 80 vol % to about 93
vol %, from about 80 vol % to about 92 vol %, from about 80 vol %
to about 91 vol %, from about 80 vol % to about 90 vol %, from
about 80 vol % to about 89 vol %, from about 80 vol % to about 88
vol %, from about 80 vol % to about 87 vol %, from about 80 vol %
to about 85 vol %, from about 80 vol % to about 82 vol %, from
about 82 vol % to about 98 vol %, from about 82 vol % to about 96
vol %, from about 82 vol % to about 95 vol %, from about 82 vol %
to about 94 vol %, from about 82 vol % to about 93 vol %, from
about 82 vol % to about 92 vol %, from about 82 vol % to about 91
vol %, from about 82 vol % to about 90 vol %, from about 82 vol %
to about 89 vol %, from about 82 vol % to about 88 vol %, from
about 82 vol % to about 87 vol %, from about 82 vol % to about 85
vol %, from about 85 vol % to about 98 vol %, from about 85 vol %
to about 96 vol %, from about 85 vol % to about 95 vol %, from
about 85 vol % to about 94 vol %, from about 85 vol % to about 93
vol %, from about 85 vol % to about 92 vol %, from about 85 vol %
to about 91 vol %, from about 85 vol % to about 90 vol %, from
about 85 vol % to about 89 vol %, from about 85 vol % to about 88
vol %, from about 85 vol % to about 87 vol %, from about 87 vol %
to about 98 vol %, from about 87 vol % to about 96 vol %, from
about 87 vol % to about 95 vol %, from about 87 vol % to about 94
vol %, from about 87 vol % to about 93 vol %, from about 87 vol %
to about 92 vol %, from about 87 vol % to about 91 vol %, to from
about 87 vol % to about 90 vol %, from about 87 vol % to about 89
vol %, from about 87 vol % to about 88 vol %, from about 88 vol %
to about 98 vol %, from about 88 vol % to about 96 vol %, from
about 88 vol % to about 95 vol %, from about 88 vol % to about 94
vol %, from about 88 vol % to about 93 vol %, from about 88 vol %
to about 92 vol %, from about 88 vol % to about 91 vol %, from
about 88 vol % to about 90 vol %, from about 88 vol % to about 89
vol %, from about 89 vol % to about 98 vol %, from about 89 vol %
to about 96 vol %, from about 89 vol % to about 95 vol %, from
about 89 vol % to about 94 vol %, from about 89 vol % to about 93
vol %, from about 89 vol % to about 92 vol %, from about 89 vol %
to about 91 vol %, from about 89 vol % to about 90 vol %, from
about 90 vol % to about 98 vol %, from about 90 vol % to about 96
vol %, from about 90 vol % to about 95 vol %, from about 90 vol %
to about 94 vol %, from about 90 vol % to about 93 vol %, from
about 90 vol % to about 92 vol %, from about 90 vol % to about 91
vol %, from about 91 vol % to about 98 vol %, from about 91 vol %
to about 96 vol %, from about 91 vol % to about 95 vol %, from
about 91 vol % to about 94 vol %, from about 91 vol % to about 93
vol %, from about 91 vol % to about 92 vol %, from about 92 vol %
to about 98 vol %, from about 92 vol % to about 96 vol %, from
about 92 vol % to about 95 vol %, from about 92 vol % to about 94
vol %, from about 92 vol % to about 93 vol %, from about 93 vol %
to about 98 vol %, from about 93 vol % to about 96 vol %, from
about 93 vol % to about 95 vol %, from about 93 vol % to about 94
vol %, from about 94 vol % to about 98 vol %, from about 94 vol %
to about 96 vol %, from about 94 vol % to about 95 vol %, or from
about 96 vol % to about 98 vol %) to form a jet-type blend having a
smoke point no more than 19.0 mm (e.g. no more than about 18.7 mm,
no more than about 18.5 mm, no more than about 18.3 mm, no more
than about 18.0 mm, no more than about 17.7 mm, no more than about
17.5 mm, no more than about 17.3 mm, or no more than about 17.0
mm); providing a hydrotreated renewable component derived from
vegetable oil, which renewable component typically comprises
triglycerides and/or fatty acids and has an aromatics content less
than about 5 vol % (e.g., less than about 4 vol %, less than about
3 vol %, less than about 2 vol %, less than about 1 vol %, less
than about 0.7 vol %, less than about 0.5 vol %, less than about
0.3 vol %, less than about 0.1 vol %, or less than about 0.05 vol
%); and blending from about 5 vol % to about 20 vol % of the
jet-type blend (e.g., from about 5 vol % to about 18 vol %, from
about 5 vol % to about 15 vol %, from about 5 vol % to to about 13
vol %, from about 5 vol % to about 12 vol %, from about 5 vol % to
about 11 vol %, from about 5 vol % to about 10 vol %, from about 5
vol % to about 9 vol %, from about 5 vol % to about 8 vol %, from
about 5 vol % to about 7 vol %, from about 5 vol % to about 6 vol
%, from about 6 vol % to about 20 vol %, from about 6 vol % to
about 18 vol %, from about 6 vol % to about 15 vol %, from about 6
vol % to about 13 vol %, from about 6 vol % to about 12 vol %, from
about 6 vol % to about 11 vol %, from about 6 vol % to about 10 vol
%, from about 6 vol % to about 9 vol %, from about 6 vol % to about
8 vol %, from about 6 vol % to about 7 vol %, from about 7 vol % to
about 20 vol %, from about 7 vol % to about 18 vol %, from about 7
vol % to about 15 vol %, from about 7 vol % to about 13 vol %, from
about 7 vol % to about 12 vol %, from about 7 vol % to about 11 vol
%, from about 7 vol % to about 10 vol %, from about 7 vol % to
about 9 vol %, from about 7 vol % to about 8 vol %, from about 8
vol % to about 20 vol %, from about 8 vol % to about 18 vol %, from
about 8 vol % to about 15 vol %, from about 8 vol % to about 13 vol
%, from about 8 vol % to about 12 vol %, from about 8 vol % to
about 11 vol %, from about 8 vol % to about 10 vol %, from about 8
vol % to about 9 vol %, from about 9 vol % to about 20 vol %, from
about 9 vol % to about 18 vol %, from about 9 vol % to about 15 vol
%, from about 9 vol % to about 13 vol %, from about 9 vol % to
about 12 vol %, from about 9 vol % to about 11 vol %, from about 9
vol % to about 10 vol %, from about 10 vol % to about 20 vol %,
from about 10 vol % to about 18 vol %, from about 10 vol % to about
15 vol %, from about 10 vol % to about 13 vol %, from about 10 vol
% to about 12 vol %, from about 10 vol % to about 11 vol %, from
about 11 vol % to about 20 vol %, from about 11 vol % to about 18
vol %, from about 11 vol % to about 15 vol %, from about 11 vol %
to about 13 vol %, or from about 11 vol % to about 12 vol %, from
about 12 vol % to about 20 vol %, from about 12 vol % to about 18
vol %, from about 12 vol % to about 15 vol %, from about 12 vol %
to about 13 vol %, from about 13 vol % to about 20 vol %, from
about 13 vol % to about 15 vol %, or from about 15 vol % to about
20 vol %) with from about 80 vol % to about 95 vol % of the
hydrotreated vegetable oil (e.g., from about 80 vol % to about 94
vol %, from about 80 vol % to about 93 vol %, from about 80 vol %
to about 92 vol %, from about 80 vol % to about 91 vol %, from
about 80 vol % to about 90 vol %, from about 80 vol % to about 89
vol %, from about 80 vol % to about 88 vol %, from about 80 vol %
to about 87 vol % from about 80 vol % to about 85 vol %, from about
80 vol % to about 82 vol %, from to about 82 vol % to about 95 vol
%, from about 82 vol % to about 94 vol %, from about 82 vol % to
about 93 vol %, from about 82 vol % to about 92 vol %, from about
82 vol % to about 91 vol %, from about 82 vol % to about 90 vol %,
from about 82 vol % to about 89 vol %, from about 82 vol % to about
88 vol %, from about 82 vol % to about 87 vol %, from about 82 vol
% to about 85 vol %, from about 85 vol % to about 95 vol %, from
about 85 vol % to about 94 vol %, from about 85 vol % to about 93
vol %, from about 85 vol % to about 92 vol %, from about 85 vol %
to about 91 vol %, from about 85 vol % to about 90 vol %, from
about 85 vol % to about 89 vol %, from about 85 vol % to about 88
vol %, from about 85 vol % to about 87 vol %, from about 87 vol %
to about 95 vol %, from about 87 vol % to about 94 vol %, from
about 87 vol % to about 93 vol %, from about 87 vol % to about 92
vol %, from about 87 vol % to about 91 vol %, from about 87 vol %
to about 90 vol %, from about 87 vol % to about 89 vol %, from
about 87 vol % to about 88 vol %, from about 88 vol % to about 95
vol %, from about 88 vol % to about 94 vol %, from about 88 vol %
to about 93 vol %, from about 88 vol % to about 92 vol %, from
about 88 vol % to about 91 vol %, from about 88 vol % to about 90
vol %, from about 88 vol % to about 89 vol %, from about 89 vol %
to about 95 vol %, from about 89 vol % to about 94 vol %, from
about 89 vol % to about 93 vol %, from about 89 vol % to about 92
vol %, from about 89 vol % to about 91 vol %, from about 89 vol %
to about 90 vol %, from about 90 vol % to about 95 vol %, from
about 90 vol % to about 94 vol %, from about 90 vol % to about 93
vol %, from about 90 vol % to about 92 vol %, from about 90 vol %
to about 91 vol %, from about 91 vol % to about 95 vol %, from
about 91 vol % to about 94 vol %, from about 91 vol % to about 93
vol %, from about 91 vol % to about 92 vol %, from about 92 vol %
to about 95 vol %, from about 92 vol % to about 94 vol %, from
about 92 vol % to about 93 vol %, from about 93 vol % to about 95
vol %, from about 93 vol % to about 94 vol %, or from about 94 vol
% to about 95 vol %) component. This blending step can
advantageously form a jet fuel composition having a smoke point of
at least 19 mm (e.g. at least about 19.3 mm, at least about 19.5
mm, at least about 19.6 mm, at least about 19.7 mm, at least about
19.8 mm, at least about 19.9 mm or at least about 20.0 mm;
additionally or alternatively, the smoke point can be no more than
about 26 mm, such as no more than about 25 mm, no more than about
24 mm, no more than about 23 mm no more than about 22 mm, no more
than about 21.5 mm, no more than about 21 mm no more than about
20.5 mm, no more than about 20 mm, or no more than about 19.8 mm)
and at least 0.5 mm (e.g., at least 0.8 mm or at least 1.0 mm)
higher than the smoke point of the jet-type blend, as well as one
or more (e.g., at least two, at least three, at least four, or all)
of the following enumerated properties: a final boiling point of at
most 300.degree. C. or at least 7.degree. C. below a final boiling
point of the jet-type blend alone; a freezing point of at most
-40.degree. C. or at least 4.degree. C. less than a freezing point
of the jet-type blend alone; a naphthalene content of at most 3.0
vol % or at least 0.3 vol % lower than a naphthalene content of the
jet-type blend alone; a JFTOT VTR rating passing the jet fuel
specification; and a sulfur content of at most 3000 wppm or at
least 150 wppm less than a sulfur content of the jet-type blend
alone.
Embodiment 13
[0083] The method of embodiment 12, wherein the jet fuel
composition has a smoke point of at least 19.5 mm, and wherein an
additional amount from about 0.5 vol % to about 3 vol % of the
heavy cat naphtha is blended with the jet fuel composition to form
a modified jet fuel composition having a smoke point between 19.0
mm and 19.2 mm, as well as a final boiling point of at most
300.degree. C., a freezing point of at most -40.degree. C., a
naphthalene content of at most 3.0 vol %, a JFTOT VTR rating
passing the jet fuel specification, and a sulfur content of at most
3000 wppm.
Embodiment 14
[0084] A blended jet fuel composition made according to the methods
of any one of the previous embodiments.
Example
[0085] A strong economic incentive exists in the winter season to
add more cracked components to jet fuel, e.g., to maximize
distillate production at the expense of lower-value products. One
example is the redirection of HCN from gasoline into jet fuel.
[0086] It has been found that blending up to .about.11.5 vol % HCN
into a jet fuel composition with a smoke point of .about.21 mm
appeared to reduce the smoke point for the blend roughly linearly
to about 17 mm. The results from two sets of samples are shown in
FIG. 1.
[0087] Smoke point is currently measured by ASTM D 1322. However,
smoke point measurement is often done with the traditional manual
method described in D 1322, which is subjective with poor
reproducibility. ASTM recently included and granted preferred
status to an automated approach in D 1322, which provides objective
smoke point measurement with a reproducibility as much as four
times better than the to manual method. The higher precision of the
automated smoke point method can be beneficial when adding cracked
components or HVO to jet fuel blends/compositions. In particular,
the automated method can eliminate much of the smoke point margin
required to ensure on-spec product with the more variable manual
method and can facilitate the use of smoke point curves, such as
shown in FIG. 1 and FIG. 2, to select the appropriate concentration
of cracked component or HVO based on the measured and targeted
smoke point of a jet fuel composition.
[0088] It was found that blending HVO into a jet fuel containing
8.0 vol % HCN appeared to increase its smoke point, as determined
by the automated test method. The addition of .about.10.0 vol % HVO
increased the smoke point by .about.1.0 mm, which allowed an
additional .about.2.9 vol % HCN to be used in a modified jet fuel
composition according to the relationship shown in FIG. 1. Such an
increase in use of HCN in jet fuel compositions can have a benefit
estimated at as much as .about.$1.3M per year (excluding the cost
of the HVO). The relationship between smoke point and HVO
concentration for this Example system is shown in FIG. 2.
[0089] While the present invention has been described and
illustrated by reference to particular embodiments, those of
ordinary skill in the art will appreciate that the invention lends
itself to variations not necessarily illustrated herein. For this
reason, then, reference should be made solely to the appended
claims for purposes of determining the enforceable scope of the
present invention.
* * * * *