U.S. patent application number 11/359690 was filed with the patent office on 2006-09-14 for biodegradable diesel fuel.
This patent application is currently assigned to Sasol Technology (PTY) Ltd.. Invention is credited to Luis Pablo Dancuart, Robert DeHaan, Ewald Watermeyer DeWet, Mark Jan Prins.
Application Number | 20060201850 11/359690 |
Document ID | / |
Family ID | 25587309 |
Filed Date | 2006-09-14 |
United States Patent
Application |
20060201850 |
Kind Code |
A1 |
DeHaan; Robert ; et
al. |
September 14, 2006 |
Biodegradable diesel fuel
Abstract
This invention relates to diesel fuel having as a component a
middle distillate cut having biodegradability properties. More
particularly, this invention relates to a diesel fuel including
middle distillates produced from a mainly paraffinic synthetic
crude which is produced by the reaction of CO and H.sub.2,
typically by the Fischer-Tropsch (FT) process. The middle
distillate according to the invention has an aromatics content of
less than 9%, as determined by the ASTM D 5186 or IP 391 test
method. The paraffinic chains of the middle distillate may be
predominantly isoparaffins.
Inventors: |
DeHaan; Robert; (Sasolburg,
ZA) ; Dancuart; Luis Pablo; (Sasolburg, ZA) ;
Prins; Mark Jan; (Sasolburg, ZA) ; DeWet; Ewald
Watermeyer; (Vanderbijlpark, ZA) |
Correspondence
Address: |
Hahn & Moodley;c/o PortfolioIP
P.O. Box 52050
Minneapolis
MN
55402
US
|
Assignee: |
Sasol Technology (PTY) Ltd.
|
Family ID: |
25587309 |
Appl. No.: |
11/359690 |
Filed: |
February 22, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09787641 |
Jun 8, 2001 |
|
|
|
11359690 |
Feb 22, 2006 |
|
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Current U.S.
Class: |
208/15 |
Current CPC
Class: |
C10G 2300/1022 20130101;
C10G 2400/04 20130101; C10G 2/32 20130101; C10L 1/08 20130101 |
Class at
Publication: |
208/015 |
International
Class: |
C10L 1/04 20060101
C10L001/04 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 5, 1998 |
ZA |
ZA 98 9037 |
Sep 17, 1999 |
WO |
PCT/ZA99/00094 |
Claims
1. A diesel fuel composition including from 10% to 100% of a
synthetic middle distillate cut having less than 9 mass %, as
determined according to IP 391 or ASTM D 5186 standards, aromatics
content, the synthetic middle distillate cut having less than 8.99
mass % monocyclic aromatics content and less than 0.01 mass %
polycyclic aromatic content, wherein the synthetic distillate is
derived from a FT primary product and the synthetic middle
distillate cut is at least 60% biodegradeable within 28 days when
using the Modified Sturm OECD method 301B.
2. A diesel fuel composition as claimed in claim 1, wherein the
synthetic middle distillate cut has an isoparaffins to n-paraffins
mass ratio of between about 1:1 to about 9:1.
3. A diesel fuel composition as claimed in claim 1, wherein the
synthetic middle distillate cut has an isoparaffins to n-paraffins
mass ratio is between about 2:1 to about 6:1.
4. A diesel fuel composition as claimed in claim 1, wherein the
synthetic middle distillate cut has an isoparaffins to n-paraffins
mass ratio is 4:1.
5. A diesel fuel composition as claimed in claim 2, wherein the
synthetic middle distillate cut comprises more than 50 mass %
isoparaffins, wherein the isoparaffins are predominantly methyl
and/or ethyl and/or propyl branched.
6. A diesel fuel composition as claimed in claim 2, wherein the
gradient of an isoparaffins to n-paraffins mass ratio profile of
the synthetic middle distillate cut increases from about 1:1 for
C.sub.8 to 8.54:1 for C.sub.15 and decrease again to about 3:1 for
C.sub.18.
7. A diesel fuel composition as claimed in claim 6, wherein a
fraction of the synthetic middle distillate cut in the C.sub.10 to
C.sub.18 carbon number range has a higher ratio of isoparaffins to
n-paraffins than a C.sub.8 to C.sub.9 fraction of the synthetic
middle distillate cut.
8. A diesel fuel composition as claimed in claim 7, wherein the
isoparaffins to n-paraffins mass ratio of the C.sub.10 to C.sub.18
fraction is between 1:1 and 9:1.
9. A diesel fuel composition as claimed in claim 6, wherein the
isoparaffins to n-paraffins mass ratio is about 8.54:1 for a
C.sub.15 fraction of the synthetic middle distillate cut.
10. A diesel fuel composition as claimed in claim 6, wherein a
C.sub.19 to C.sub.24 fraction of the middle distillate cut has a
mass ratio range of isoparaffins to n-paraffins of between 3.3:1
and 5:1.
11. A diesel fuel composition as claimed in claim 10, wherein the
C.sub.19 to C.sub.24 fraction of the middle distillate cut has a
mass ratio range of isoparaffins to n-paraffins of between 4:1 and
4.9:1.
12. A diesel fuel composition as claimed in claim 6, wherein the
mass ratio of isoparaffins to n-paraffins is adjusted by
controlling the blend ratio of hydrocracked to straight run
components of the synthetic middle distillate cut.
13. A diesel fuel composition as claimed in claim 12, wherein the
isoparaffins to n-paraffins mass ratio of the C.sub.10 to C.sub.18
fraction having 30 mass % straight run component is between 1:1 and
2:5:1.
14. A diesel fuel composition as claimed in claim 12, wherein the
isoparaffins to n-paraffins mass ratio of the C.sub.10 to C.sub.18
fraction having 20 mass % straight run component is between 1.5:1
and 3:5:1.
15. A diesel fuel composition as claimed in claim 12, wherein the
isoparaffins to n-paraffins mass ratio of the C.sub.10 to C.sub.18
fraction having 10 mass % straight run component is between 2.3:1
and 4.3:1.
16. A diesel fuel composition as claimed in claim 12, wherein the
isoparaffins to n-paraffins mass ratio of the C.sub.10 to C.sub.18
fraction having substantially only a hydrocracked component is
between 4:1 and 9:1.
17. A diesel fuel composition as claimed in claim 5, wherein at
least some of the isoparaffins are di-methyl branched.
18. A diesel fuel composition as claimed in claim 5, wherein at
least 30 mass % of the isoparaffins are mono-methyl branched.
19. A diesel fuel composition as claimed in claim 18, wherein at
least some of the isoparaffins are ethyl branched.
20. A diesel fuel composition as claimed in claim 1, including from
0 to 90 mass % of at least one other diesel fuel.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of application Ser. No.
09/787,641, filed Jun. 6, 2001, which claims priority to Patent
Cooperation Treat (PCT) International Application Number
PCT/ZA99/00094 having an International Filing Date of Sep. 17,
1999, which claims priority to a Foreign Application Number ZA 98
9037 having a Foreign Filing Date of Oct. 5, 1998.
FIELD OF THE INVENTION
[0002] This invention relates to middle distillates having
biodegradability properties and to a process for production of such
distillates. More particularly, this invention relates to middle
distillates produced from a mainly paraffinic synthetic crude which
is produced by the reaction of CO and H.sub.2, typically by the
Fischer-Tropsch (FT) process.
BACKGROUND TO THE INVENTION
[0003] In recent years a trend has developed to produce products
which are so called "environmentally friendly", one aspect of which
is biodegradability. To this end various bodies, such as ISO and
the OECD have developed test methods to quantify biodegradability.
One such test is the CO.sub.2 evolution test method, also known as
the modified Sturm OECD method 301B, which test for ready
biodegradability. In terms of this test, compounds can be
considered to be readily biodegradable if they reach 60%
biodegradation within 28 days.
[0004] Currently available middle distillates, typically crude oil
derived diesel fuels, such as US 2-D grade (low sulphur No. 2-D
grade for diesel fuel oil as specified in ASTM D 975-94) and/or
CARB (California Air Resources Board 1993 specification) grade
diesel, do not meet the biodegradability requirements of the
abovementioned biodegradability test.
[0005] The prior art teaches in ZA 96/9890 that high
biodegradability of hydrocarbon base oils could be derived from the
presence of predominantly mono-methyl branching on the paraffinic
carbon backbone. U.S. Pat. No. 5,498,596 discloses a non-toxic,
biodegradable well fluid comprising 98% (mass) n-paraffins and less
than 1% (mass) monocyclic aromatics as well as other olefinic
components. The biodegradability of the well fluid in the U.S.
patent can not be related back to the nature of the paraffinic
molecules due to the fact that biodegradability is enhanced through
branching and not through linear n-paraffinic molecules.
[0006] A need thus exists for a middle distillate cut, typically a
diesel fuel, which is readily biodegradable as determined by the
abovementioned biodegradability test.
SUMMARY OF THE INVENTION
[0007] Thus, according to a first aspect of this invention, there
is provided a biodegradable middle distillate cut, such as a diesel
fuel, having an aromatics content of less than 9 mass %, as
determined by the ASTM D 5186 or IP 391 test method.
[0008] The synthetic middle distillate cut may have less than 8.99
mass % monocyclic aromatics content.
[0009] The synthetic middle distillate cut may have less than 0.01
mass % polycyclic aromatics.
[0010] The synthetic middle distillate cut may have an isoparaffins
to n-paraffins mass ratio of between about 1:1 to about 12:1,
typically the isoparaffins to n-paraffins mass ratio is between
about 2:1 to about 6:1, and in one embodiment is 4:1.
[0011] The synthetic middle distillate cut may be a FT process
product, or be at least partially produced in accordance with the
FT process and/or process philosophy.
[0012] According to a second aspect of the invention, the synthetic
middle distillate cut includes more than 50 mass % isoparaffins,
wherein the isoparaffins consist predominantly of methyl and/or
ethyl and/or propyl branched isoparaffins.
[0013] The gradient of an isoparaffins to n-paraffins mass ratio
profile of the synthetic middle distillate cut may increase from
about 1:1 for C.sub.8 to 8.54:1 for C.sub.15 and decrease again to
about 3:1 for C.sub.18.
[0014] Typically, a fraction of the synthetic middle distillate cut
in the C.sub.10 to C.sub.18 carbon number range has a higher ratio
of isoparaffins to n-paraffins than a C.sub.8 to C.sub.9 fraction
of the synthetic middle distillate cut.
[0015] The isoparaffins to n-paraffins mass ratio of the C.sub.10
to C.sub.18 fraction may be between 1:1 and 9:1.
[0016] The isoparaffins to n-paraffins mass ratio may be 8.54:1 for
a C.sub.15 fraction of the synthetic middle distillate cut.
[0017] A C.sub.19 to C.sub.24 fraction of the middle distillate cut
may have a narrow mass ratio range of isoparaffins to n-paraffins
of between 3.3:1 and 5:1, generally between 4:1 and 4.9:1.
[0018] The mass ratio of isoparaffins to n-paraffins may be
adjusted by controlling the blend ratio of hydrocracked to straight
run components of the synthetic middle distillate cut. Thus, the
isoparaffins to n-paraffins mass ratio of the C.sub.10 to C.sub.18
fraction having 30 mass % straight run component may be between 1:1
and 2:5:1.
[0019] The isoparaffins to n-paraffins mass ratio of the C.sub.10
to C.sub.18 fraction having 20 mass % straight run component may be
between 1.5:1 and 3:5:1.
[0020] The isoparaffins to n-paraffins mass ratio of the C.sub.10
to C.sub.18 fraction having 10 mass % straight run component may be
between 2.3:1 and 4.3:1.
[0021] The isoparaffins to n-paraffins mass ratio of the C.sub.10
to C.sub.18 fraction having substantially only a hydrocracked
component may be between 4:1 and 9:1
[0022] At least some of the isoparaffins of the middle distillate
cut may be methyl branched.
[0023] Typically, wherein at least some of the isoparaffins are
di-methyl branched.
[0024] In a useful embodiment, at least 30 mass % of the
isoparaffins are mono-methyl branched.
[0025] Some of the isoparaffins may be ethyl branched, or even
propyl branched. TABLE-US-00001 TABLE A Comparison of the Branching
Characteristics of Blends of SR, HX and SPD Diesels SR Diesel HX
Diesel SPD-Diesel n-Paraff I-Paraff Total n-Paraff I-Paraff Total
n-Paraff I-Paraff Total C8 1.07 1.07 0.38 0.38 0.58 0.58 C9 22.64
1.57 24.21 1.86 5.37 7.23 6.01 3.60 9.61 C10 14.73 1.74 16.47 1.90
8.43 10.33 6.48 6.12 12.60 C11 5.43 0.32 5.75 1.60 8.75 10.35 6.13
6.31 12.44 C12 11.79 0.67 12.46 1.41 8.88 10.29 6.57 5.94 12.51 C13
11.16 0.65 11.81 1.32 8.46 9.78 6.31 6.03 12.34 C14 11.66 0.70
12.36 1.27 8.95 10.22 6.41 5.82 12.23 C15 9.19 0.46 9.65 1.03 8.80
9.83 4.98 4.97 9.95 C16 4.94 0.31 5.25 0.96 6.38 7.34 2.58 3.53
6.11 C17 0.88 0.88 0.88 3.92 4.80 0.76 2.33 3.09 C18 0.08 0.08 0.90
2.73 3.63 0.66 1.93 2.59 C19 0.60 2.69 3.29 0.38 1.47 1.85 C20 0.54
2.38 2.92 0.32 0.78 1.10 C21 0.56 2.73 3.29 0.29 0.72 1.01 C22 0.60
2.12 2.72 0.29 0.53 0.82 C23 0.41 1.93 2.34 0.25 0.40 0.65 C24 0.23
0.92 1.15 0.16 0.38 0.54 C25 0.14 0.14 Total 93.57 6.42 99.99 16.45
83.58 100.03 49.16 50.86 100.02 In the table: SPD--Sasol Slurry
Phase Distillate SR--Straight Run HX--Hydrocracked
[0026] TABLE-US-00002 TABLE B Branching Characteristics of Blends
of SR & HX Diesels iso: normal Paraffins Ratio (mass) SR Diesel
(mass) 0% 10% 20% 30% C8 0.0 0.0 0.0 0.0 C9 2.9 1.3 0.8 0.5 C10 4.4
2.4 1.6 1.1 C11 5.5 4.0 3.0 2.3 C12 6.3 3.3 2.1 1.4 C13 6.4 3.3 2.1
1.4 C14 7.0 3.5 2.2 1.5 C15 8.5 4.3 2.7 1.8 C16 6.6 4.3 2.9 2.1 C17
4.5 4.0 3.6 3.1 C18 3.0 3.0 3.0 2.9 C19 4.5 4.5 4.5 4.5 C20 4.4 4.4
4.4 4.4 C21 4.9 4.9 4.9 4.9 C22 3.5 3.5 3.5 3.5 C23 4.7 4.7 4.7 4.7
C24 4.0 4.0 4.0 4.0 C25
[0027] The above table is represented graphically in FIG. 2.
[0028] According to a third aspect of the invention, there is
provided a biodegradable synthetic middle distillate cut, having an
aromatics content substantially as described above.
[0029] According to a fourth aspect of the invention, there is
provided a biodegradable synthetic middle distillate cut, having an
isoparaffinic content substantially as described above.
[0030] The invention extends to a biodegradable synthetic middle
distillate cut, having an isoparaffinic content and an aromatics
content substantially as described above.
[0031] The biodegradable synthetic distillate may be a FT
product.
[0032] According to a fifth aspect of the invention, there is
provided a biodegradable diesel fuel composition including from 10
mass % to 100 mass % of a middle distillate cut as described
above.
[0033] The biodegradable diesel fuel composition may include from 0
to 90 mass % of another diesel fuel, such as conventional
commercially available diesel fuel.
[0034] The biodegradable diesel fuel composition may include from 0
to 10 mass % additives.
[0035] The additives may include a lubricity improver.
[0036] The lubricity improver may comprise from 0 to 0.5 mass % of
the composition, typically from 0.00001 mass % to 0.05 mass % of
the composition. In a particularly useful embodiment, the lubricity
improver comprises from 0.00 mass 8% to 0.02 mass % of the
composition.
[0037] The biodegradable diesel fuel composition may include a
crude oil derived diesel, such as US 2-D grade diesel fuel and/or
CARB grade diesel fuel, as the other diesel fuel of the
composition.
[0038] According to yet another aspect of the invention, there is
provided a process for producing a readily biodegradable synthetic
middle distillate, the process including: [0039] (a) separating the
products obtained from synthesis gas via the FT synthesis reaction
into one or more heavier fraction and one or more lighter fraction;
[0040] (b) catalytically processing the heavier fraction under
conditions which yield mainly middle distillates; [0041] (c)
separating the middle distillate product of step (b) from a light
product fraction and a heavier product fraction which are also
produced in step (b); and [0042] (d) blending the middle distillate
fraction obtained in step (c) with at least a portion of the one or
more lighter fraction of step (a), or products thereof.
[0043] The catalytic processing of step (b) may be a
hydroprocessing step, for example, hydrocracking.
[0044] The process for producing a synthetic middle distillate may
include one or more additional step of fractionating at least some
of the one or more lighter fraction of step (a), or products
thereof, prior to step (d).
[0045] The process for producing a synthetic middle distillate may
include the additional step of hydrotreating at least some of the
one or more light fraction of step (a), or products thereof, prior
to step (d).
[0046] The one or more heavier fraction of step (a) may have a
boiling point above about 270.degree. C., however, it may be above
300.degree. C.
[0047] The one or more lighter fraction may have a boiling point in
the range C.sub.5 to the boiling point of the heavier fraction,
typically in the range 160.degree. C. to 270.degree. C.
[0048] The product of step (d) may boil in the range 100.degree. C.
to 400.degree. C. The product of step (d) may boil in the range
160.degree. C. to 370.degree. C.
[0049] The product of step (d) may be obtained by mixing the middle
distillate fraction obtained in step (c) with at least a portion of
the one or more lighter fraction of step (a), or products thereof,
in a volume ratio of between 1:1 and 9:1, typically 2:1 and 6:1,
and in one embodiment, in a volume ratio of 84:16.
[0050] The product of the above process may be a synthetic middle
distillate cut, or products thereof, or compositions thereof, as
described above.
[0051] The product of step (d) may be a diesel fuel.
[0052] A biodegradable diesel fuel produced in accordance with this
invention may be produced from a mainly paraffinic synthetic crude
(syncrude) obtained from synthesis gas (syngas) through a reaction
like the FT reaction.
[0053] The FT products cover a broad range of hydrocarbons from
methane to species with molecular masses above 1400; including
mainly paraffinic hydrocarbons and much smaller quantities of other
species such as olefins and oxygenates. Such a diesel fuel could be
used on its own or in blends to improve the quality of other diesel
fuels not meeting the current and/or proposed, more stringent fuel
quality and environmental specifications.
[0054] The invention extends to an essentially non-polluting,
readily biodegradable diesel fuel composition comprising of a
mixture of normal paraffins (n-paraffins) and iso-paraffins in the
typical diesel range from 160-370.degree. C., having an
iso-paraffin:n-paraffin mass ratio from about 2:1 to about 12:1,
more typically from 2:1 to 6:1, and the iso-paraffins of the
mixture contain greater than 30 mass %, based on the total mass of
the iso-paraffins in the mixture, of mono-methyl species, with the
balance consisting mainly of ethyl and/or dimethyl branched
species. These iso-paraffins contained in a mixture with minor
amounts of aromatics and other materials, contribute to a product
from which readily biodegradable diesel fuels can be obtained.
[0055] This diesel will readily biodegrade in an aquatic
environment under aerobic conditions. This biodegradability can be
attributed to the very low aromatic content present in the middle
distillate cut, typically a diesel fuel. The aromatic content will
typically comprise 2.5% (mass) of monocyclic, 0.2% (mass) of
dicyclic and <10 ppm (mass) of polycyclic aromatics with a total
aromatic content of around 2.7% (mass).
DESCRIPTION OF THE DRAWINGS
[0056] In the drawings,
[0057] FIG. 1 shows a flow sheet of a Fischer-Tropsch process for
producing a diesel fuel composition of the present invention;
[0058] FIG. 2 shows a graph representing the branching
characteristics of a diesel fuel composition of the present
invention; and
[0059] FIG. 3 shows a graph representing the results of the
Modified Sturm test for the biodegradeability of diesel fuels
carried out on the diesel fuel composition of the invention.
SPECIFIC DESCRIPTION OF THE INVENTION
Process
[0060] The process of this invention provides a process for the
conversion of primary FT products into naphtha and middle
distillates, specifically high performance diesel.
[0061] The FT process is used industrially to convert synthesis
gas, derived from coal, natural gas, biomass or heavy oil streams,
into hydrocarbons ranging from methane to species with molecular
masses above 1400. While the main products are linear paraffinic
materials, other species such as branched paraffins, olefins and
oxygenated components form part of the product slate. The exact
product slate depends on reactor configuration, operating
conditions and type of catalyst that is employed, as is evident
from e.g. Catal. Rev. -Sci. Eng., 23(1&2), 265-278 (1981).
[0062] Typical reactors for the production of heavier hydrocarbons
(i.e. waxy hydrocarbons) are the Slurry Bed or the Tubular Fixed
Bed types, while typical operating conditions are 160-280.degree.
C., in some cases 210-260.degree. C., and 18-50 Bar, in some cases
20-30 Bar. Active metals typically useable in the catalyst used in
such a reactor include iron, ruthenium or cobalt. While each
catalyst will give its own unique product slate, in all cases the
product contains some waxy, highly paraffinic material which needs
to be further upgraded into usable products. The FT products can be
converted into a range of final products, such as middle
distillates, gasoline, solvents, lube oil bases, etc. Such
conversion, which usually consists of a range of processes such as
hydrocracking, hydrotreatment and distillation, can be termed a FT
work-up process.
[0063] The FT work-up process of this invention uses a feed stream
consisting of C.sub.5 and higher hydrocarbons derived from a FT
process. This feed is separated into at least two individual
fractions, a heavier and at least one lighter fraction. The cut
point between the two fractions is usually less than 300.degree. C.
and typically around 270.degree. C.
[0064] The table below gives a typical composition of the two
fractions, within about 10% accuracy: TABLE-US-00003 TABLE 1
Typical Fischer-Tropsch product after separation into two fractions
Condensate Wax Boiling range (<270.degree. C., volume %)
(>270.degree. C., volume %) C.sub.5-160.degree. C. 45
160-270.degree. C. 51 3 270-370.degree. C. 4 35 370-500.degree. C.
42 >500.degree. C. 20
[0065] The >270.degree. C. fraction, also referred to as wax,
contains a considerable amount of hydrocarbon material, which boils
higher than the normal diesel range. If we consider a diesel
boiling range of 100-400.degree. C., typically 160-370.degree. C.,
it means that all material heavier than about 370.degree. C. needs
to be converted into lighter materials by means of a catalytic
process often referred to as hydrocracking. Catalysts for this step
are of the bifunctional type; i.e. they contain sites active for
cracking and for hydrogenation.
[0066] Catalytic metals active for hydrogenation include group VIII
noble metals, such as platinum or palladium, or sulphided Group
VIII base metals, e.g. nickel, cobalt, which may or may not include
a sulphided Group VI metal, e.g. molybdenum. The support for the
metals can be any refractory oxide, such as silica, alumina,
titania, zirconia, vanadia and other Group III, IV, VA and VI
oxides, alone or in combination with other refractory oxides.
Alternatively, the support can partly or totally consist of
zeolite. Amorphous silica-alumina is the preferred support for
middle distillates conversion.
[0067] Process conditions for hydrocracking can be varied over a
wide range and are usually laboriously chosen after extensive
experimentation to optimise the yield of middle distillates. In
this regard, it is important to note that, as in many chemical
reactions, there is a trade-off between conversion and selectivity.
A very high conversion will result in a high yield of gases and low
yield of distillate fuels. It is therefore important to
painstakingly tune the process conditions in order to limit the
conversion of >370.degree. C. hydrocarbons. Table 2 lists some
of the conditions found, after extensive experimentation, to
provide a desirable product range. TABLE-US-00004 TABLE 2 Typical
Hydrocracking Process Conditions Broad Preferred Process Condition
Range Range Temperature, .degree. C. 150-450 340-400 Pressure,
bar(g) 10-200 30-80 Hydrogen Flow Rate, 100-2000 800-1600
m.sup.3.sub.n/m.sup.3 feed Conversion of >370.degree. C.
material, 30-80 50-70 Mass %
[0068] It will be clear to those skilled in the art that it is
possible to convert all the >370.degree. C. material in the
feedstock by recycling the part that is not converted during the
hydrocracking process.
[0069] As is evident from table 1, most of the fraction boiling
below 270.degree. C. is already boiling in the typical boiling
range for diesel, i.e. 160-370.degree. C. This fraction may or may
not be subjected to hydrotreating. By hydrotreating, heteroatoms
are removed and unsaturated compounds are hydrogenated.
Hydrotreating is a well-known industrial process catalysed by any
catalyst having a hydrogenation function, e.g. Group VIII noble
metal or a sulphided base metal or sulphided Group VI metals, or
combinations thereof. Preferred supports are alumina and silica.
Table 3 lists typical operating conditions for the hydrotreating
process. TABLE-US-00005 TABLE 3 Typical Hydrotreating Process
Conditions Broad Preferred Process Condition Range Range
Temperature, .degree. C. 150-450 200-400 Pressure, bar(g) 10-200
30-80 Hydrogen Flow Rate, m.sup.3.sub.n/m.sup.3 feed 100-2000
400-1600
[0070] While the hydrotreated fraction may be fractionated into
paraffinic materials useful as solvents, the applicant has now
found that the hydrotreated fraction may be directly blended with
the products obtained from hydrocracking the wax. Although it is
possible to hydroisomerise the material contained in the condensate
stream, the applicant has found that this leads to a small, but
significant loss of material in the diesel boiling range to lighter
material. Furthermore, isomerisation leads to the formation of
branched isomers, which leads to Cetane ratings less than that of
the corresponding normal paraffins (n-paraffins).
[0071] Several diesel fuels, produced broadly in accordance with
the invention, as well as other crude oil derived diesel fuels such
as US 2-D grade and CARB grade, were tested by the applicant. The
basic characteristics of the fuels tested for biodegradability are
included in Table 4(a).
[0072] Synthetic diesel fuels, produced broadly in accordance with
this invention, and other conventional diesels were tested by the
applicant. It was found that there were significant differences
regarding the chemical composition of the fuels.
[0073] In particular, the synthetic fuels contained very small
quantities of aromatic species. Other differences relate to the
predominance of paraffinic species in the synthetic diesels, as can
be seen from Table 4(b).
[0074] Upon analysis, it thus appears, since most of the other
characteristics of the synthetic and conventional diesel fuels are
not very dissimilar, the difference in the biodegradability
performance can be attributed to the differences in the chemical
nature indicated above. TABLE-US-00006 TABLE 4(a) Basic
Characteristics of the Tested Fuels CARB* SPD Diesel SPD Diesel
Commercial US Protocol Fuel Name Type A Type B 2D Standard Fuel
Code S1 S2 P1 P2 Density (15.degree. C.) Kg/dm.sup.3 0.7769 0.7779
0.8547 0.8308 Distillation ASTM D86 IBP .degree. C. 189 185 184 203
10% .degree. C. 209 208 214 218 50% .degree. C. 256 257 259 249 90%
.degree. C. 331 332 312 290 FBP .degree. C. 356 358 342 351 HPLC
Modified 0.47% 0.35% 32.78% 6.65% Aromatics IP 391 (mass %) Method
Monocyclic Mass % of 93.62% N/A 71.35% 99.55% HPLC Aromatics
Bicyclic Mass % of 6.38% N/A 25.84% 0.45% HPLC Aromatics Polycyclic
Mass % of <0.01% N/A 2.81% <0.01% HPLC Aromatics Oxygen (mass
%) N/D 0.3% N/D N/D Sulphur ASTM 0.001% 0.002% 0.022% 0.028% (mass
%) D4294 *CARB--California Air Resources Board
[0075] Furthermore, in a specific middle distillate produced in
accordance with this invention, the total amount of isoparaffins in
the light boiling range of the diesel (160-270.degree. C. fraction)
and the heavier range of the diesel (270.degree. C.-370.degree. C.)
are shown in the following Table 4(b). TABLE-US-00007 TABLE 4(b)
Isoparaffins: n-Paraffins of Middle Distillate Fractions Average
Iso: Normal Boiling Corresponding Paraffins Ratio Range Carbon
Range Range Typical value 160-270.degree. C. C.sub.10-C.sub.17
0.5-4.0 2.2 270-370.degree. C. C.sub.17-C.sub.23 4.0-14.0 10.5
[0076] It is this unique composition of the synthetic fuel, which
is directly caused by the way in which the FT work-up process of
this invention is operated, that contributes to the unique
characteristics of said middle distillates.
[0077] The applicant has also found, that from the perspective of
fuel quality, it is not necessary to hydrotreat the <270.degree.
C. fraction, adding said fraction directly to the products from
hydrocracking the wax. While this results in the inclusion of
oxygenates and unsaturates in the final diesel, fuel specifications
usually allow for this. Circumventing the need for hydrotreatment
of the condensate results in considerable savings of both capital
and operating cost.
[0078] The invention will now be illustrated, by way of
non-limiting examples only, with reference to the accompanying FIG.
1.
[0079] A FT work-up process is outlined in the attached FIG. 1. The
synthesis gas (syngas), a mixture of Hydrogen and Carbon Monoxide,
enters the FT reactor 1 where the synthesis gas is converted to
hydrocarbons by the FT process.
[0080] A lighter FT fraction is recovered in line 7, and may or may
not pass through fractionator 2 and hydrotreater 3. The product 9
(9a) from the hydrotreater may be separated in fractionator 4 or,
alternatively, mixed with hydrocracker 5 products 16 and sent to a
common fractionator 6.
[0081] A waxy FT fraction is recovered in line 13 and sent to
hydrocracker 5. If fractionation 2 is considered then the bottoms
cut 12 are also sent to hydrocracker 5. The products 16, on their
own or mixed with the lighter fraction 9a, are separated in
fractionator 6.
[0082] Depending on the process scheme, a light product fraction,
naphtha 19, is obtained from fractionator 6 or by blending
equivalent fractions 10 and 17. This is a C.sub.5.sub.-160.degree.
C. fraction useful as naphtha.
[0083] A somewhat heavier cut i.e. the middle cut, synthetic diesel
20, is obtainable in a similar way from fractionator 6 or by
blending equivalent fractions 11 and 18. This cut is recovered as a
160-370.degree. C. fraction useful as diesel
[0084] The heavy unconverted material 21 from fractionator 6 is
recycled to extinction to hydrocracker 5. Alternatively, the
residue may be used for production of synthetic lube oil bases. A
small amount of C.sub.1-C.sub.4 gases is also separated in
fractionator 6.
[0085] The described FT work-up process of FIG. 1 may be combined
in a number of configurations. The applicant considers these an
exercise in what is known in the art as Process Synthesis
Optimisation.
[0086] However, the specific process conditions for the Work-up of
Fischer-Tropsch primary products, the possible process
configurations of which are outlined in Table 5, were obtained
after extensive and laborious experimentation and design.
TABLE-US-00008 TABLE 5 Possible Fischer-Tropsch Product Work-up
Process Configurations Process Configuration Process Step A B C D E
F 2 Light FT Product Fractionator X X 3 Light FT Product
Hydrotreater X X X X 4 Hydrotreater Products Fractionator X X X 5
Waxy FT Product Hydrocracker X X X X X X 6 Hydrocracked Products
Fractionator X X X X X X Number Reference numerals of FIG. 1 FT
Fischer-Tropsch
Experimental Procedure
[0087] The biodegradability of the fuels was tested using the
Carbon Dioxide Evolution method (modified Sturm OECD Method 301B).
This method tests for ready biodegradability. A compound can be
considered readily biodegradable if it reaches 60% biodegradation
within 28 days under the prescribed test conditions. Domestic
activated sludge, not previously exposed to industrial effluent,
was used as the source of micro-organisms for the test. The
biodegradability tests were continuously validated using Sodium
acetate as a reference chemical for checking the viability of the
micro-organisms
[0088] The test involves aerating the sample by passing carbon
dioxide-free air at a controlled rate in the dark or in diffuse
light. The sample must be the only source of carbon. Degradation is
followed over 28 days by determining the carbon dioxide produced.
This gas is trapped in barium or sodium hydroxide, and it is
measured by titration of the residual hydroxide or as inorganic
carbon. For additional details refer to the standard procedure.
[0089] The results of the tests are set out in table 6 and chart 1
below. TABLE-US-00009 TABLE 6 Biodegradability of Diesel Fuels
(Modified Sturm Test) Synthetic Petroleum Days Diesels Diesels from
start of SPD A SPD B US 2D CARB test sequence S1 S2 P1 P2 0 0% 0%
0% 0% 2 4% 4% 2% 2% 5 12% 11% 4% 7% 9 22% 19% 14% 15% 13 31% 23%
18% 16% 15 39% 30% 23% 20% 19 45% 39% 26% 22% 22 48% 41% 28% 24% 27
58% 53% 32% 27% 28 62% 60% 34% 35% 28 61% 63% 34% 37%
[0090] The above table is represented graphically in FIG. 3.
EXAMPLES
Example 1
[0091] Fuel S1 was produced broadly in accordance with the
invention, by following the process described above. It is a fully
hydroprocessed fuel. The fractionation of the two basic components
was completed in separate steps. S1 diesel was a blend of 84% (vol)
of hydrocracked diesel (product stream 11 from fractionator 4) and
16% (vol) of hydrotreated diesel (product stream 18 from
fractionator 6) produced using configuration B of Table 5. It
contained 2.68% total aromatics, most of the aromatics species
being monocyclic.
[0092] This fuel biodegraded 61% after 28 days under the conditions
specified for the described modified Sturm OECD Method 301 B. A
fuel with this behaviour is considered biodegradable.
Example 2
[0093] Fuel S2 was produced by hydrocracking of the FT wax and
distilling the diesel fraction (product stream 18). The primary
light FT products were distilled separately (product stream 11
produced without passing through hydrotreater 3). S2 diesel was
obtained by blending these two cuts in a 84:16 ratio (volume).
Process Configuration C of Table 5 was used to produce this fuel.
The total aromatics content was 2.46%.
[0094] This fuel biodegraded 63% after 28 days under the same
conditions described in example 1. This fuel can also be considered
biodegradable.
Example 3
[0095] Fuel P1 is a commercial diesel procured in the United States
of America. It meets the US 2D diesel specification. This
conventional petroleum based diesel fuel contained 38.22%
aromatics, almost 71% of which were monocyclic species.
[0096] This fuel biodegraded 34% under the conditions described in
example 1. A fuel with this behaviour is not considered
biodegradable.
Example 4
[0097] Fuel P2 is a non-commercial fuel procured in the United
States of America. It meets the specifications of the California
Air Resources Board (CARB) protocol. This fuel contained 9.91%
aromatics, mainly monocyclic species. In spite of this, this fuel
biodegraded only ca 37% under the conditions described in example
1.
[0098] A fuel with this behaviour is not considered
biodegradable.
* * * * *