CA2405780C - Low sulfur, low emission blends of fischer-tropsch and conventional diesel fuels - Google Patents
Low sulfur, low emission blends of fischer-tropsch and conventional diesel fuels Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
Abstract
A blended fuel, useful as a diesel fuel, wherein the fuel blend contains an undercut conventional diesel fuel, blended with a Fischer-Tropsch derived diesel fuel, such that the blend demonstrates better than expected emissions and a reduced sulfur content. In particular, the blend is an asymmetric diesel fuel blend comprising a Fischer-Tropsch derived hydrocarbon distillate having a T95 of at least 600 ~F, blended with a petroleum derived hydrocarbon distillate having an initial boiling point and a T95 no greater than 640 ~F.
Description
LO'V~T S'1~,FUR. LO'~' EMISSION $1JENDS OF F1SCHER-TROPSCH
AND CON'VENTIONA.L DTESEL FUF~,S
FIELD OF TT~3E TNVENTTON
This invention rel$tes to blends of Fischer-Tropsch derived fuels and conventional petroleum fuels. Moxe particularly, this invention relates to a blended fuel, useful in a diesel engine which is low in sulfur and demonstrates better than predicted emissions characteristics.
BACKGROI:JND
A concern for Future diesel ftiels is the ability to produce higher quality and cleaner burning diesel fuels without extensive and expensive reprocessing.
Typical factors detrimental to fuel quality are high sulfur, high density, high end boiling and T95 points, (the temperature at which most all the material has boiled off, leaving only 5°,ro remaining in the distillation pat) high aromatic and polyaxomatic contents. These factors have been shown to have a detrimental, effect on emissions. For example, see the Coordinating Research Council (CRC) study on heavy duty diesels in the United States reported in SAE pap~xs 932735, 950250 and 950251, and the European Programme on Emissions, Fuels and Engine Technologies (.h.PEFE) study on light and heavy duty diesels reported in SAE papers 961069, 961Q74 and 9b1075.
In co~atrast, emissions measurements on Fischer-~,'ropsch diesel fuels, which. have virtually nil sulfur, aromatic and polyaromatic contents demonstrate favorable emissions characteristics. A report by the Southwest Research Institute (SwRT) entitled "Tlxe Standing of Fischer~Tropseh Diesel .ift an Assay of -Z-Fuel Performance and Emissions" by 3ime11 Brwin and Thomas W. Ryan, TrT, NRIrL (National Renewable Energy Laboratory) Subcontract YZ-2-113215, October 1.993, details the advantage of Fischer-.Tropseh fuels for lowering emissions when used neat, that is, use of pure Fischer-'I'ropsch diesel fuels.
Presently, there remains a need to develop an economic, low sulfur distillate fuel blend useful as a diesel fuel which has lowered emissions after combustion and allows a greater portion of the distillate to be used as a high value prerniuua product. ~n particular, sulfur levels, emissions of solid particulate matter (PM), and nitrogen oxides (NOx) are important due to current and proposed environmental regulations. While it has been disclosed that Fiseher-Tropsch fuels can be blended with conventional fuels, see for example U.S. Patent No. 5,689,031 herein incorporated by reference, the ability to further improve such blends with respect to emissions provides a distinct economic advantage.
The citations of the several SAB papers referenced herein are:
p.x. Zemroch, P. Schirnmering, G. Sado, C.T. Gray and Hans-Martin Burghardt, "European .Pragramme on Emissions, .Fuels and Engine Technologies-Statistical Design and Analysis Techniques ", SAE paper 961069.
M. Signer, P. ~Ieinze, R. Mercogliano and J.f. Stein, "European Programme on Emissions, x'uels and Engine Technologies-Heavy Duty Diesel Study", SAE
paper 96x074.
D.J. Rickeard, R. Bonettt~ and M. Signer, ", "Eurapean Programme on Emissions, Fuels and Engine Technologies-Comparison of Light and Heavy Duty Diesels", SAE paper 961075.
T~.B. Spreen, T.~..1;f11man anal R.L. Mason, ",Effects of Cetane Number, AromatiCS and Oxygenates on Emissions fro»t a x994 D"eatry-Duty Diesel Engine with Exhausr Catalyst", SAE paper 9S02S0.
T~.B. Spreen, T.l... IJlIman and R.L, Mason, "L~',f,~ects of Cetane Number on Emissions front a Prototype 1998 heavy Duty Diesel Engine ", S,AE pager 950251.
Thomas Ryan III and Tixn,ell Erwin, "Diesel Fued Composition Effect on Ignation and Emissions", SAE paper 932735.
M. I-lublin, P.G. Gadd, D.E. Hall, ~.P. Schindler, "European Programme on Emissions, Fuels and Engine ~"echnologies-Light Duty Diesel Str~dy ", SA'E
paper 961073.
S'U'MMAR'Y' 41~ TTY INVENTION
According to an embodiment of this invention is provided a blended fuel, useful as a diesel fuel, wherein. the fuel blend contains an undercut conventional diesel fuel, blended wifih a Fischer-Tropsch derived diesel fuel, such that the bleed demonstrates better than expected emissions and a reduced sulfur content, Tn particular, the blend is an asymmetric diesel fuel blend comprising a Fischea-Tropsch derived hydrocarbon distillate haring a T95 of at least 600° F
(316° C), preferably at least 6S0° F (343° C), more preferably at least 700-750° F (371° C-399° C), blended with a petroleum derived hydrocarbon distillate~having an initial bo'~ling point and a T95 no greater than 640° F (37S°
C), preferably a T9S
no greater than 600° F (316° C) wherein the blend has a sulfur content of less than 500 wppm. The resultant diesel fuel blend is characterized by an initial boiling point ranging from at least 280° F+ (I3S ° C+), preferably at least 300°
F+ (X49° C~-), more preferably 320° F+ (I60° C-~) and a T95 up to about 700° F
(371 ° C), preferably up to about 680° F (360° C), even more preferably up to about 660° F (349° C), still more preferably up to about 640° F (378° C) and contains:
Sulfur < 500 wppm, preferably < 150 wppm, more preferably < 50 wppm, even more preferably < 30 ~'PPm~
Polyaromatics < 11 wt %, preferably < wt 5 %, more preferably < 1 Wt %, Cetane number > 50, preferably > 55, more preferably >60, Density from about 0.79 to about 0.85 wherein the Fiseher-Tropseh disdliate comprises 5-90 ~vol. % of the blended diesel duel, preferably 2050 vol. %, more preferably 30-$0 vol. %.
A typical diesel fuel boils in the range of about 320-700° F.
FIowever, sulfur levels generally increase with boiling point, i.e., heavier diesel derived from crude oil has a higher sulfur content than lighter diesel, See Jirnell Frwin, Thomas W. Ryan, III, "The Standing of Fischer-Tropsch Diesel in an Assay of Fuel Performance and Emissions ", NRET. (1~'ational Renewable Energy I,abvratory) Subcontract ,Y'Z-2-113215, ,October 1993. The blend of the invention provides a fuel having reduced sulfur levels and emissions levels lower than those predicted by standard correlations, e.g., lauropean program on Emissions Fuels and ~x~gine Technologies, SAE Paper 96x073, by elirninatting the heavy end of the conventional diesel fuel and replacing the heavy end with a low sulfur Fischer-Tropsch derived diesel fuel boiling above the range of a normal diesel fuel. Tn addition to reducing sulfur levels, the diesel fuel blend of this invention outperform predicted emissions levels, especially in emissions of nitrous oxides.
_$_ DETAILED DESCRIPTxOIV' OF THE INVENTTON
The Fischer.-Tropseh process is well known to those ska,lled in the art, see foz~ example, U.S. Patent Nos. 5,34$,982 and 5,545,674 herein incorporated by reference. Typically the Fischer Tropsch process involves the reaction of a synthesis gas feed comprising hydrogen and carbon xr~onoxide fed into a hydrocarbon synthesis reactor in the presence of a Fischer-Tropseh catalyst, generally a supported or unsupported Group VIII, non-noble metal e.g., Fe, Ni, Ru, Co and with or without a promoter e.g., ruthenium., rhenium and zirconium.
These processes include fixed bed, fluid bed and slurry hydrocarbon synthesis.
A preferred Fiseher-Tropsch process is one that utilizes a non-shifting catalyst, such as cobalt or ruthenium or mixtures thereof, preferably cobalt, and preferably a promoted cobalt, the promoter being zirconium or rhenium, preferably rhenium. Such catalysts are well known and a preferred catalyst is described in U.S. Patent loo. 4,565,663 as vsrell as European Patent 0 266 898.
The synthesis gas feed used in the process comprises a mixture of I~2 arid CO
wherein PI~:CO are present in a ratio of at-least about 1.7, preferably at least about 1.75, more preferably 1.75 to 2.5.
Regardless of the catalyst or conditions employed however, the high proportion of normal paraffins in the product produced by the Fiseher-Tropsch process must be converted from wa~cy hydrocarbon feeds into more useable products, such as transportation fuels. Thus, conv~xsion is accomplished primarily by hydrogen treatments involving hydrotreating, hydroisomerixation, and hydrocracking in which a suitable fraction of the product is contacted with a suitable catalyst in the presence of hydrogen to isomerize the fraction by converting the molecular structure of at least a portion of the hydrocarbon material from normal paraff'ms to branched iso-paraffins to form the desired product, as is known to those skilled in the art.
~6-fiydroisomerization and hydroeracking are well known processes for upgrading hydrocarbon synthesis products and their conditions can vary widely.
I3ydroisomerization is achieved by reacting the waxy feed with hydrogen in the presence of a suitable hydoisomerization catalyst. While many catalysts ma.y be satisfactory for this step, some catalysts perform. better than others and are preferred. For example, applicants preferred hydroisomerization catalyst comprises one or more Group 'Vl'Tr noble or non-noble metal components, and depending on the reaction conditions, one or more non-noble metals such as Co, Ni and Fe, which may or may not also include a Group YIB metal (e.g., Mo, Wj oxide promoters, supported on an acidic metal oxide support to give the catalyst both a hydrogenation and dehydrogenation function for activating the hydrocarbons and an acid function fvr isvmerization. However, noble metals reduce hydrogenolysis, particularly at lower temperatures and will therefore be preferred for some applications. preferred noble metals are Pt and Pd. The catalyst may also contain a Group TB metal, such as copper, as a hydrogenolysis suppressant. The cracking and hydrogenating activity of the catalyst .is deternZined by its specific composition. The metal Grroups referred to herein are those found in the Sargent 'Welch Periodic Table of the Elements, copyright 1968.
The acidic support is preferably an amozphous silica-alumina where the silica is present in amounts of less than about 30 wt %a, preferably S-30 wt %, more preferably 10-20 wt %. Additionally; the silica-aluxnina support may contain amounts of a binder for maintaining catalyst integrity during high temperature, high pressure processes. Typical binders include silica, alumi.na, Group IVA metal oxides, e.g., zirconia, titania, various types of clays, magnesia, etc., and mixtures of the foregoing, preferably alumina, silica, or zirconia, nnost preferably alurnina. Binders, when present in the catalyst composition, make up ..
about 5-50% by weight of the support, preferably 5-35% by weight, more preferably 20-30% by weight.
Characteristics of the support preferably include surface areas of 200-500 m2 /gm (BET' method), preferably about 2S0-400 m,2 /gm; and pore volume of less than 1, xxrl/gm as determined by water adsorption, preferably in the range of about 0.35 to 0.8 m/gm, e.g., 0. 57 ml/gm.
The metals may be incorporated onto the support by any suitable method, and the incipient wetness technique is preferred. Suitable metal solutions may be used, such as nickel nitrate, copper nitrate or other aqueous soluble salts.
Preferably, the metals are co-impregnated onto the support allowing for intimate contact between the Cmup VIII metal and the Group ~ metal, for example, the formation of bimetallic clusters. The impregnated support is then dried, e.g., over night at about 100°-1S0° C., followed by calcination in air at temperatures ranging from about 200°-550° C., preferably 350°-550° C., so that there is no excessive loss of surface a~cea or pore volume.
Grroup VnI metal concentrations of less than about 1 S wt °k based on total weight of catalyst, preferably abort 1-1.2 wt %, more preferably about I-10 wt %
can be employed. The Group TB metal is usually present in lessEr amounts and may range from about a 1:2 to about a 1:20 ratio respecting the Grroup VIII
metal.
Nevertheless, the Fischer-Tropsch derived distillates that may be used in the blends of this inven'don include distillates recovered from the Fischer-Tropsch reactor, whether or not hydrotreated, i.e., hydrogen treatments in the presence of a suitable catalyst, including but not limited to, one or more of hydrotreating, hydroisomerization, de~cwa~cir~g and hydrocrack'mg, as well as _$,.
distillates recovered from fractionating the wax containing product from the Fischer-Tropsch reactor, whether or not hydrotreated. however, a preferred Fischer-Tropsch derived distillate comprises a distillate fraction derived from any hydroisomerized wax containing Fischer-Tropsch feed utilizing any suitable hydroisomerization catalyst under standard hydroisomerization conditions commonly known in the art.
Preferably, the Fischer-Tropsch derived hydrocarbon distillate has a T95 of at least 600°F, more preferably the Fischer-Tropsch derived distillate has an initial boiling point of at least 300° F and a T95 of at least 650°F, even more preferably an initial boiling point of at least 320°F and a T95 of at least 700-750°
1~ and contains:
Sulfur, nitrogen < 10 wppm, preferably < S wppm, more preferably < 1 wppm, .Aromatics < I wt %, preferably < 0.1 wt %, more preferably undetectable by ASTM A-5292 Cetane number _> 6~, preferably >_ 70, The conventional petroleum derived fuel may be any conventional low sulfur diesel fuel, i.e., low sulfrxr No. 2-D diesel fuel as specified in ASTM
D-97S-98b, which may be derived from crude oil by conventional petroleum processing ar from slack wax or from other fEed stocks, and is characterized as an undercut diesel fuel, that is, a fuel that has a final cut point below the boiling range of a typical diesel fuel. Preferably, the undercut conventional blend stock of this invention has a T95 no greater than 640°F, preferably a T95 below 600°
F. however, because sulfur level increases with boiling point, cut points may be varied, i.e., decreased, to achieve desired sulfur levels in the conventional blend stock. rn this way, sulfur levels of the final blend may be controlled based on the final cut point of the conventional diesel blend stock.
A better illustration of the preferred exnboditneztts of this invention may be had by the following comparisons and exaauples.
A diesel fuel blend v~ras prepared by combining an undercut conventional low sczlfur No. 2-D diesel fuel {ASTM D975-9Sb) with a Fischer-Tropsch derived diesel fuel blend stock.
The Fischer-Tropsch distihate blend stock was prepared as follows:
A 300° F-~ Fischer-Tropsch derived wax containing feed was rug, through tyro 0.5 in, up-f7.ow f~.xed bed reactors, R~ and R2, connected in series and contained within an isothermal sand bath where the product of the first reactor (R1) was fed directly into the reaction zone of the second reactor (RZ).
l~I contained 80 ee (44.7 gms) of a commercially available hydroisomerization catalyst comprising 0.5 wt% Pd on a silica-alumin.a support containing nominally 20 wt % alumina/80 wt% silica and 30 wt% alumina binder. R2 contained a catalyst blend eontain~ing 29 cc (Id.2 gms) of a commercially a~railable dewaxing catalyst comprising 0.5 wt% Pt ou an extrudate containing Theta-1 zeolite {T'~l~ and S 1 cc (27.5 gms) of the hydroisomerization catalyst contained in Rl. The extrudate was crushed and the -S, +20 mesh used to load a portion of the fixed bed reactor. There was no treatment or interstage stripping of the hydroisomerized product of Rl prior to feeding into R2.
The 300° F+ wax feed was run through R1 xunning at conditions that result in about SO% conversion of the 700° F~- material to 700°
F- and dewaxing was nzn through R.2 to achieve a cloud point Iess than -20° C. The isothermal reactor conditions were as follows: 715 psig, 1650 SCF/Bbl hydrogen treat rate at 0.854 LHSV and a temperature of approximately 606° p'.
Product distribution from the process detailed above is shown in Table 1 below and the boiling point cuts used in the p'ischEr-Tropsch blend stock are indicated as Fuel Z. The feed was obtained by reacting hydrogen and CO over a Fischer-Tropseh catalyst comprising cobalt and rhenium on a titanic support.
Tn particular, Fuel s comprised a 300-S00° F ~'ischer-Tropsch derived hydrocarbon distillate fraction.
TABLE 1.
BOILINGr RANGrE 'Y'TELD, WT% FCJEL 1 IBP - 280F 10.492 No 2$0-300F 2.744 No 300-looF s~.s~9 700-800F 10.016 'Yes 800F~- 23. I49 No By virtue of using the Fischer-Txopsch process, the Fischer-Tropsch derived distillate has essentially nil sulfur and nitrogen. Further, the process does not make aromatics and polyarornatics, or as usually operated, virtually no aromatics are produced. Some olefins at~d oxygenates may be produced since one of the pathways for the production of paraffins is through an olefinic interoaediate. Preferably, olefin concentration in the Fischer-Tropsch derived distillate is leSS than 10 vol %, snore preferably less than 5 voi %, even more preferably less than 1 vol % (ASTM A-2710). Nevertheless, olefin and -~1-oxygenate concentration are relatively lo~v, and essentially nil after hydrotreatment.
The undercrxt conventional diesel fuel vcvas a U.S. No. 2-D low sulfur diesel fuel (ASTM D975-98b). In particular, the conventional diesel fuel comprised an undercut diesel fuel which has a nominal boiling range of aboufi 320-640° F and is indicated as Fuel 2. Sulfur levels listed in Table 2 were determined using ASTM D-2622.
'TA~3~$ 2 $DILING RANGrE YIELD, ~VT%O FUEL 2 Sulfur, wppm IBP - 600F 61.43 'yes 22 600-625F 1 x.48 Yes 238 62S-640F 6.03 Yes 6S5 640-650F 3.81 No 1054 650-660F 4.44. No 1632 660-6751~ 9.69 No 1834 The entire conventional diesel (1BP 675° F) qualifies as a low sulfur diesel, i.e., the sulfur levels are < O.OS% of the total fuel by weight, as designated in ASTM D975-~8b and contains 417 wppm of sulfur, whereas the undercut diesel (T~l'-640° F), lei 2, contains only 104 wppm. Thus, as illustrated from the fractions contained in Table 2, sulfur level increases with boiling range.
A 50/50 blend of the heavy Fischex-Tropsch diesel (FuEl 1) and the undercut conventional diesel (Fuel 2) was prepared for engine testing and is indicated as Fuel 3.
- z2 -For emissions testing, the combined fuel blend was compared with two conventional petroleum diesel fuels referred to hereafter as Fuel ~. an,d Fuel 5.
Fuel 4 was a IJ.S. No.2-D low sulfur diesel fuel (ASTM D975-98b) and Fuel 5 was a European Low Sulfur Automotive diesel (LSAD(J). Table 3 below provides a comparison of the rele~rant characteristics for Fuels 3-S.
Density (~-3ss) .8090 ,846 .854 Sulfur, % (1~D <0.1% 0.04% 0.05%
~s~io) IBP, C (ATM p-SG) 179 197 1$4 'r$0, C (ASTM D-$6)~$0 294 2$$
T95, C ~AS~rM D..s6)355 339 345 Cetane (AST~D-s~.3)61.5 ~ 53,0 50.1 Aromatics, total 14.6 27.9 26.7 %
(IP-391) Polyaromatics, 0. $ 7. i 6.4 %
(IP-391) Clo~xd Point, C - I9 - 6 - 5 (ASTM D-5771) CFPP, C (~-309) - 26 - 7 - I 8 Each standard analytical technique used to determine the components of Fuels 3-5 is shown in parentheses. Table 3 illustrates that the blend of the invention has significantly lower sulfur levels as compared to each of the conventional fuels.
.Lh3'"G.rN''.E TESTING
For comparison, the blended diesel fuel of the invention (Fuel 3) was compared vcrith the conventional petroleum fuels. The fuels were evaluated with a Peugeot 405 Indirect injection (TDI) light duty diesel engine. regulated emissions were measured during hot start transient cycles and emissions of hydrocarbons {HC), carbon monoxide {CO), nitrous oxide (NOx) and particulate matter (PIvI) were measured. The results are summarized in Table 4 below. Test data is represented as the absolute value in gmrHp-hr ~vhieh is followed by the percent change for each emission value verses the base, Fuel 5; a conventional petroleum diesel fuel. All fuels were run through the combined Urban Drive Cycle and Extra Urban Drive Cycle (commonly known as ECE-EUDC
respectively) hot and cold test protocols in duplicate-in a randomized design.
The light duty European test cycle is performed in two parts;
ECE: this urban cycle represents inner city driving conditions after a cold start with a maximum speed of 50 l~n~lh, and EUDC: the extra-urban driving cycle is typical of suburban and ope~t road driving behavior and includes speeds up to 120 km/h. The data is based an the combined emissions of the LCE and EUDC cycles expressed in glkm. See SAE
Papers 9610'3 and 961068.
Fuel 5 was used as the reference and therefore run in triplicate; all other fuels were run in duplicate. ~'he data represents the average values from the combination of the ECE-EUDC test procedures ("combined ECErEUDC"
z~eporting method).
'Z'Al3T...L 4 HC Delta NOx Delta CO Delta 1'1VI Delta Fuel 3 0.05 -X5.8% 0.58 -13. I % 0.43 -41.8 % 0.045 -41.3 Fuel4 0.103 -12.5% 0.644 -3.4% 0.650 ,11.6% 0.076 -1.5%
Fuel s 0.118 basis 0.669 basis 0.736 basis 0.077 basis The data, revealed Significantly lower etxrissions produced from apglicants' diesel fuel blend, ~.e13, than observed with either of the conventional diesel fuels (Fuels 4 and 5). ~n particular, applicants blend, Fuel 3 produced emissions with a SS.8% decxease in hydrocarbons, 4I.8% decrease in carbon monoxide, 13.1% decrease in nitrogen oxides and 4I.3% decrease in, particulate matter as compared to the base conventional diesel fuel. However, a closer review of the data, shows that the fuels of this invention have a substantial advantage in particulates and nilrogex~ oxides emissions above that which world be expected.
See SAE 96I074 and 961075. In this regard, it is well known in the art that the most critical emissions parameter for a diesel fuel is the P1VI-NOx trade-off, i.e., there is a known inverse relationship between particulate matter and NOx. See SAE 961,074 and 961075. Thus, in regard to emissions, decreasiug one variable will normally result in increasing the other variable.
Table 5 below details the predicted changes for light duty (i.e., passenger car) diesel engines according to the well recognized ~.'uropean program on Emissions, Fuels and Engine Technologies (EPEFE) study in Europe undertaken by the government, auto and oil companies to define the relationship between ~15-fuel properties and erxiissions based on variables in density, cetane number and T95; see SAE Paper 961073, Tables 3 through 6. The left hand column indicates the two pollutants (particulate matter and nitrogen oxides) along with the changes in absolute emissions in g/,13p-hr and percent change (%
increase(positive) or % decrease(negative)) for each of the four fuel characteristics shown at the top of the columns. The emission change (in g/Hp-hr and percent) is based on a deviation of one of the four fuel characteristics as shown in parenthesis. For example, if the T95 was lowered by SS° C, the particulate emissions would decrease by 6.9% while the NOx would increase by 4.6%.
TABLE S
I7ensit~ Polyaromatics Cetane T95 (-0.027) (-7% +8 numbers) (55C) k'azticulate p..hr ,0.012 -0.003 0.003 -0.004 % -19.1.% -5.2% S.2% -6.9%
NOx g/Hp-hr 0.008 -O.O i 9 -0.001 0.026 % I.4!o -3.4% -0.2% 4.6%a Table 6 below was produced by combining the published results of Table 5, with the properties measured in. Table 3 and the emissions results of Table 4.
The resulting test data indicates the e~,Pected change ire emissions as projected by the EPEFE equations rrersus the actual changes measured during emissions testing on each of the fuels listed in Table 5, Again, all results are referenced to Puel 4 as the base fuel.
AND CON'VENTIONA.L DTESEL FUF~,S
FIELD OF TT~3E TNVENTTON
This invention rel$tes to blends of Fischer-Tropsch derived fuels and conventional petroleum fuels. Moxe particularly, this invention relates to a blended fuel, useful in a diesel engine which is low in sulfur and demonstrates better than predicted emissions characteristics.
BACKGROI:JND
A concern for Future diesel ftiels is the ability to produce higher quality and cleaner burning diesel fuels without extensive and expensive reprocessing.
Typical factors detrimental to fuel quality are high sulfur, high density, high end boiling and T95 points, (the temperature at which most all the material has boiled off, leaving only 5°,ro remaining in the distillation pat) high aromatic and polyaxomatic contents. These factors have been shown to have a detrimental, effect on emissions. For example, see the Coordinating Research Council (CRC) study on heavy duty diesels in the United States reported in SAE pap~xs 932735, 950250 and 950251, and the European Programme on Emissions, Fuels and Engine Technologies (.h.PEFE) study on light and heavy duty diesels reported in SAE papers 961069, 961Q74 and 9b1075.
In co~atrast, emissions measurements on Fischer-~,'ropsch diesel fuels, which. have virtually nil sulfur, aromatic and polyaromatic contents demonstrate favorable emissions characteristics. A report by the Southwest Research Institute (SwRT) entitled "Tlxe Standing of Fischer~Tropseh Diesel .ift an Assay of -Z-Fuel Performance and Emissions" by 3ime11 Brwin and Thomas W. Ryan, TrT, NRIrL (National Renewable Energy Laboratory) Subcontract YZ-2-113215, October 1.993, details the advantage of Fischer-.Tropseh fuels for lowering emissions when used neat, that is, use of pure Fischer-'I'ropsch diesel fuels.
Presently, there remains a need to develop an economic, low sulfur distillate fuel blend useful as a diesel fuel which has lowered emissions after combustion and allows a greater portion of the distillate to be used as a high value prerniuua product. ~n particular, sulfur levels, emissions of solid particulate matter (PM), and nitrogen oxides (NOx) are important due to current and proposed environmental regulations. While it has been disclosed that Fiseher-Tropsch fuels can be blended with conventional fuels, see for example U.S. Patent No. 5,689,031 herein incorporated by reference, the ability to further improve such blends with respect to emissions provides a distinct economic advantage.
The citations of the several SAB papers referenced herein are:
p.x. Zemroch, P. Schirnmering, G. Sado, C.T. Gray and Hans-Martin Burghardt, "European .Pragramme on Emissions, .Fuels and Engine Technologies-Statistical Design and Analysis Techniques ", SAE paper 961069.
M. Signer, P. ~Ieinze, R. Mercogliano and J.f. Stein, "European Programme on Emissions, x'uels and Engine Technologies-Heavy Duty Diesel Study", SAE
paper 96x074.
D.J. Rickeard, R. Bonettt~ and M. Signer, ", "Eurapean Programme on Emissions, Fuels and Engine Technologies-Comparison of Light and Heavy Duty Diesels", SAE paper 961075.
T~.B. Spreen, T.~..1;f11man anal R.L. Mason, ",Effects of Cetane Number, AromatiCS and Oxygenates on Emissions fro»t a x994 D"eatry-Duty Diesel Engine with Exhausr Catalyst", SAE paper 9S02S0.
T~.B. Spreen, T.l... IJlIman and R.L, Mason, "L~',f,~ects of Cetane Number on Emissions front a Prototype 1998 heavy Duty Diesel Engine ", S,AE pager 950251.
Thomas Ryan III and Tixn,ell Erwin, "Diesel Fued Composition Effect on Ignation and Emissions", SAE paper 932735.
M. I-lublin, P.G. Gadd, D.E. Hall, ~.P. Schindler, "European Programme on Emissions, Fuels and Engine ~"echnologies-Light Duty Diesel Str~dy ", SA'E
paper 961073.
S'U'MMAR'Y' 41~ TTY INVENTION
According to an embodiment of this invention is provided a blended fuel, useful as a diesel fuel, wherein. the fuel blend contains an undercut conventional diesel fuel, blended wifih a Fischer-Tropsch derived diesel fuel, such that the bleed demonstrates better than expected emissions and a reduced sulfur content, Tn particular, the blend is an asymmetric diesel fuel blend comprising a Fischea-Tropsch derived hydrocarbon distillate haring a T95 of at least 600° F
(316° C), preferably at least 6S0° F (343° C), more preferably at least 700-750° F (371° C-399° C), blended with a petroleum derived hydrocarbon distillate~having an initial bo'~ling point and a T95 no greater than 640° F (37S°
C), preferably a T9S
no greater than 600° F (316° C) wherein the blend has a sulfur content of less than 500 wppm. The resultant diesel fuel blend is characterized by an initial boiling point ranging from at least 280° F+ (I3S ° C+), preferably at least 300°
F+ (X49° C~-), more preferably 320° F+ (I60° C-~) and a T95 up to about 700° F
(371 ° C), preferably up to about 680° F (360° C), even more preferably up to about 660° F (349° C), still more preferably up to about 640° F (378° C) and contains:
Sulfur < 500 wppm, preferably < 150 wppm, more preferably < 50 wppm, even more preferably < 30 ~'PPm~
Polyaromatics < 11 wt %, preferably < wt 5 %, more preferably < 1 Wt %, Cetane number > 50, preferably > 55, more preferably >60, Density from about 0.79 to about 0.85 wherein the Fiseher-Tropseh disdliate comprises 5-90 ~vol. % of the blended diesel duel, preferably 2050 vol. %, more preferably 30-$0 vol. %.
A typical diesel fuel boils in the range of about 320-700° F.
FIowever, sulfur levels generally increase with boiling point, i.e., heavier diesel derived from crude oil has a higher sulfur content than lighter diesel, See Jirnell Frwin, Thomas W. Ryan, III, "The Standing of Fischer-Tropsch Diesel in an Assay of Fuel Performance and Emissions ", NRET. (1~'ational Renewable Energy I,abvratory) Subcontract ,Y'Z-2-113215, ,October 1993. The blend of the invention provides a fuel having reduced sulfur levels and emissions levels lower than those predicted by standard correlations, e.g., lauropean program on Emissions Fuels and ~x~gine Technologies, SAE Paper 96x073, by elirninatting the heavy end of the conventional diesel fuel and replacing the heavy end with a low sulfur Fischer-Tropsch derived diesel fuel boiling above the range of a normal diesel fuel. Tn addition to reducing sulfur levels, the diesel fuel blend of this invention outperform predicted emissions levels, especially in emissions of nitrous oxides.
_$_ DETAILED DESCRIPTxOIV' OF THE INVENTTON
The Fischer.-Tropseh process is well known to those ska,lled in the art, see foz~ example, U.S. Patent Nos. 5,34$,982 and 5,545,674 herein incorporated by reference. Typically the Fischer Tropsch process involves the reaction of a synthesis gas feed comprising hydrogen and carbon xr~onoxide fed into a hydrocarbon synthesis reactor in the presence of a Fischer-Tropseh catalyst, generally a supported or unsupported Group VIII, non-noble metal e.g., Fe, Ni, Ru, Co and with or without a promoter e.g., ruthenium., rhenium and zirconium.
These processes include fixed bed, fluid bed and slurry hydrocarbon synthesis.
A preferred Fiseher-Tropsch process is one that utilizes a non-shifting catalyst, such as cobalt or ruthenium or mixtures thereof, preferably cobalt, and preferably a promoted cobalt, the promoter being zirconium or rhenium, preferably rhenium. Such catalysts are well known and a preferred catalyst is described in U.S. Patent loo. 4,565,663 as vsrell as European Patent 0 266 898.
The synthesis gas feed used in the process comprises a mixture of I~2 arid CO
wherein PI~:CO are present in a ratio of at-least about 1.7, preferably at least about 1.75, more preferably 1.75 to 2.5.
Regardless of the catalyst or conditions employed however, the high proportion of normal paraffins in the product produced by the Fiseher-Tropsch process must be converted from wa~cy hydrocarbon feeds into more useable products, such as transportation fuels. Thus, conv~xsion is accomplished primarily by hydrogen treatments involving hydrotreating, hydroisomerixation, and hydrocracking in which a suitable fraction of the product is contacted with a suitable catalyst in the presence of hydrogen to isomerize the fraction by converting the molecular structure of at least a portion of the hydrocarbon material from normal paraff'ms to branched iso-paraffins to form the desired product, as is known to those skilled in the art.
~6-fiydroisomerization and hydroeracking are well known processes for upgrading hydrocarbon synthesis products and their conditions can vary widely.
I3ydroisomerization is achieved by reacting the waxy feed with hydrogen in the presence of a suitable hydoisomerization catalyst. While many catalysts ma.y be satisfactory for this step, some catalysts perform. better than others and are preferred. For example, applicants preferred hydroisomerization catalyst comprises one or more Group 'Vl'Tr noble or non-noble metal components, and depending on the reaction conditions, one or more non-noble metals such as Co, Ni and Fe, which may or may not also include a Group YIB metal (e.g., Mo, Wj oxide promoters, supported on an acidic metal oxide support to give the catalyst both a hydrogenation and dehydrogenation function for activating the hydrocarbons and an acid function fvr isvmerization. However, noble metals reduce hydrogenolysis, particularly at lower temperatures and will therefore be preferred for some applications. preferred noble metals are Pt and Pd. The catalyst may also contain a Group TB metal, such as copper, as a hydrogenolysis suppressant. The cracking and hydrogenating activity of the catalyst .is deternZined by its specific composition. The metal Grroups referred to herein are those found in the Sargent 'Welch Periodic Table of the Elements, copyright 1968.
The acidic support is preferably an amozphous silica-alumina where the silica is present in amounts of less than about 30 wt %a, preferably S-30 wt %, more preferably 10-20 wt %. Additionally; the silica-aluxnina support may contain amounts of a binder for maintaining catalyst integrity during high temperature, high pressure processes. Typical binders include silica, alumi.na, Group IVA metal oxides, e.g., zirconia, titania, various types of clays, magnesia, etc., and mixtures of the foregoing, preferably alumina, silica, or zirconia, nnost preferably alurnina. Binders, when present in the catalyst composition, make up ..
about 5-50% by weight of the support, preferably 5-35% by weight, more preferably 20-30% by weight.
Characteristics of the support preferably include surface areas of 200-500 m2 /gm (BET' method), preferably about 2S0-400 m,2 /gm; and pore volume of less than 1, xxrl/gm as determined by water adsorption, preferably in the range of about 0.35 to 0.8 m/gm, e.g., 0. 57 ml/gm.
The metals may be incorporated onto the support by any suitable method, and the incipient wetness technique is preferred. Suitable metal solutions may be used, such as nickel nitrate, copper nitrate or other aqueous soluble salts.
Preferably, the metals are co-impregnated onto the support allowing for intimate contact between the Cmup VIII metal and the Group ~ metal, for example, the formation of bimetallic clusters. The impregnated support is then dried, e.g., over night at about 100°-1S0° C., followed by calcination in air at temperatures ranging from about 200°-550° C., preferably 350°-550° C., so that there is no excessive loss of surface a~cea or pore volume.
Grroup VnI metal concentrations of less than about 1 S wt °k based on total weight of catalyst, preferably abort 1-1.2 wt %, more preferably about I-10 wt %
can be employed. The Group TB metal is usually present in lessEr amounts and may range from about a 1:2 to about a 1:20 ratio respecting the Grroup VIII
metal.
Nevertheless, the Fischer-Tropsch derived distillates that may be used in the blends of this inven'don include distillates recovered from the Fischer-Tropsch reactor, whether or not hydrotreated, i.e., hydrogen treatments in the presence of a suitable catalyst, including but not limited to, one or more of hydrotreating, hydroisomerization, de~cwa~cir~g and hydrocrack'mg, as well as _$,.
distillates recovered from fractionating the wax containing product from the Fischer-Tropsch reactor, whether or not hydrotreated. however, a preferred Fischer-Tropsch derived distillate comprises a distillate fraction derived from any hydroisomerized wax containing Fischer-Tropsch feed utilizing any suitable hydroisomerization catalyst under standard hydroisomerization conditions commonly known in the art.
Preferably, the Fischer-Tropsch derived hydrocarbon distillate has a T95 of at least 600°F, more preferably the Fischer-Tropsch derived distillate has an initial boiling point of at least 300° F and a T95 of at least 650°F, even more preferably an initial boiling point of at least 320°F and a T95 of at least 700-750°
1~ and contains:
Sulfur, nitrogen < 10 wppm, preferably < S wppm, more preferably < 1 wppm, .Aromatics < I wt %, preferably < 0.1 wt %, more preferably undetectable by ASTM A-5292 Cetane number _> 6~, preferably >_ 70, The conventional petroleum derived fuel may be any conventional low sulfur diesel fuel, i.e., low sulfrxr No. 2-D diesel fuel as specified in ASTM
D-97S-98b, which may be derived from crude oil by conventional petroleum processing ar from slack wax or from other fEed stocks, and is characterized as an undercut diesel fuel, that is, a fuel that has a final cut point below the boiling range of a typical diesel fuel. Preferably, the undercut conventional blend stock of this invention has a T95 no greater than 640°F, preferably a T95 below 600°
F. however, because sulfur level increases with boiling point, cut points may be varied, i.e., decreased, to achieve desired sulfur levels in the conventional blend stock. rn this way, sulfur levels of the final blend may be controlled based on the final cut point of the conventional diesel blend stock.
A better illustration of the preferred exnboditneztts of this invention may be had by the following comparisons and exaauples.
A diesel fuel blend v~ras prepared by combining an undercut conventional low sczlfur No. 2-D diesel fuel {ASTM D975-9Sb) with a Fischer-Tropsch derived diesel fuel blend stock.
The Fischer-Tropsch distihate blend stock was prepared as follows:
A 300° F-~ Fischer-Tropsch derived wax containing feed was rug, through tyro 0.5 in, up-f7.ow f~.xed bed reactors, R~ and R2, connected in series and contained within an isothermal sand bath where the product of the first reactor (R1) was fed directly into the reaction zone of the second reactor (RZ).
l~I contained 80 ee (44.7 gms) of a commercially available hydroisomerization catalyst comprising 0.5 wt% Pd on a silica-alumin.a support containing nominally 20 wt % alumina/80 wt% silica and 30 wt% alumina binder. R2 contained a catalyst blend eontain~ing 29 cc (Id.2 gms) of a commercially a~railable dewaxing catalyst comprising 0.5 wt% Pt ou an extrudate containing Theta-1 zeolite {T'~l~ and S 1 cc (27.5 gms) of the hydroisomerization catalyst contained in Rl. The extrudate was crushed and the -S, +20 mesh used to load a portion of the fixed bed reactor. There was no treatment or interstage stripping of the hydroisomerized product of Rl prior to feeding into R2.
The 300° F+ wax feed was run through R1 xunning at conditions that result in about SO% conversion of the 700° F~- material to 700°
F- and dewaxing was nzn through R.2 to achieve a cloud point Iess than -20° C. The isothermal reactor conditions were as follows: 715 psig, 1650 SCF/Bbl hydrogen treat rate at 0.854 LHSV and a temperature of approximately 606° p'.
Product distribution from the process detailed above is shown in Table 1 below and the boiling point cuts used in the p'ischEr-Tropsch blend stock are indicated as Fuel Z. The feed was obtained by reacting hydrogen and CO over a Fischer-Tropseh catalyst comprising cobalt and rhenium on a titanic support.
Tn particular, Fuel s comprised a 300-S00° F ~'ischer-Tropsch derived hydrocarbon distillate fraction.
TABLE 1.
BOILINGr RANGrE 'Y'TELD, WT% FCJEL 1 IBP - 280F 10.492 No 2$0-300F 2.744 No 300-looF s~.s~9 700-800F 10.016 'Yes 800F~- 23. I49 No By virtue of using the Fischer-Txopsch process, the Fischer-Tropsch derived distillate has essentially nil sulfur and nitrogen. Further, the process does not make aromatics and polyarornatics, or as usually operated, virtually no aromatics are produced. Some olefins at~d oxygenates may be produced since one of the pathways for the production of paraffins is through an olefinic interoaediate. Preferably, olefin concentration in the Fischer-Tropsch derived distillate is leSS than 10 vol %, snore preferably less than 5 voi %, even more preferably less than 1 vol % (ASTM A-2710). Nevertheless, olefin and -~1-oxygenate concentration are relatively lo~v, and essentially nil after hydrotreatment.
The undercrxt conventional diesel fuel vcvas a U.S. No. 2-D low sulfur diesel fuel (ASTM D975-98b). In particular, the conventional diesel fuel comprised an undercut diesel fuel which has a nominal boiling range of aboufi 320-640° F and is indicated as Fuel 2. Sulfur levels listed in Table 2 were determined using ASTM D-2622.
'TA~3~$ 2 $DILING RANGrE YIELD, ~VT%O FUEL 2 Sulfur, wppm IBP - 600F 61.43 'yes 22 600-625F 1 x.48 Yes 238 62S-640F 6.03 Yes 6S5 640-650F 3.81 No 1054 650-660F 4.44. No 1632 660-6751~ 9.69 No 1834 The entire conventional diesel (1BP 675° F) qualifies as a low sulfur diesel, i.e., the sulfur levels are < O.OS% of the total fuel by weight, as designated in ASTM D975-~8b and contains 417 wppm of sulfur, whereas the undercut diesel (T~l'-640° F), lei 2, contains only 104 wppm. Thus, as illustrated from the fractions contained in Table 2, sulfur level increases with boiling range.
A 50/50 blend of the heavy Fischex-Tropsch diesel (FuEl 1) and the undercut conventional diesel (Fuel 2) was prepared for engine testing and is indicated as Fuel 3.
- z2 -For emissions testing, the combined fuel blend was compared with two conventional petroleum diesel fuels referred to hereafter as Fuel ~. an,d Fuel 5.
Fuel 4 was a IJ.S. No.2-D low sulfur diesel fuel (ASTM D975-98b) and Fuel 5 was a European Low Sulfur Automotive diesel (LSAD(J). Table 3 below provides a comparison of the rele~rant characteristics for Fuels 3-S.
Density (~-3ss) .8090 ,846 .854 Sulfur, % (1~D <0.1% 0.04% 0.05%
~s~io) IBP, C (ATM p-SG) 179 197 1$4 'r$0, C (ASTM D-$6)~$0 294 2$$
T95, C ~AS~rM D..s6)355 339 345 Cetane (AST~D-s~.3)61.5 ~ 53,0 50.1 Aromatics, total 14.6 27.9 26.7 %
(IP-391) Polyaromatics, 0. $ 7. i 6.4 %
(IP-391) Clo~xd Point, C - I9 - 6 - 5 (ASTM D-5771) CFPP, C (~-309) - 26 - 7 - I 8 Each standard analytical technique used to determine the components of Fuels 3-5 is shown in parentheses. Table 3 illustrates that the blend of the invention has significantly lower sulfur levels as compared to each of the conventional fuels.
.Lh3'"G.rN''.E TESTING
For comparison, the blended diesel fuel of the invention (Fuel 3) was compared vcrith the conventional petroleum fuels. The fuels were evaluated with a Peugeot 405 Indirect injection (TDI) light duty diesel engine. regulated emissions were measured during hot start transient cycles and emissions of hydrocarbons {HC), carbon monoxide {CO), nitrous oxide (NOx) and particulate matter (PIvI) were measured. The results are summarized in Table 4 below. Test data is represented as the absolute value in gmrHp-hr ~vhieh is followed by the percent change for each emission value verses the base, Fuel 5; a conventional petroleum diesel fuel. All fuels were run through the combined Urban Drive Cycle and Extra Urban Drive Cycle (commonly known as ECE-EUDC
respectively) hot and cold test protocols in duplicate-in a randomized design.
The light duty European test cycle is performed in two parts;
ECE: this urban cycle represents inner city driving conditions after a cold start with a maximum speed of 50 l~n~lh, and EUDC: the extra-urban driving cycle is typical of suburban and ope~t road driving behavior and includes speeds up to 120 km/h. The data is based an the combined emissions of the LCE and EUDC cycles expressed in glkm. See SAE
Papers 9610'3 and 961068.
Fuel 5 was used as the reference and therefore run in triplicate; all other fuels were run in duplicate. ~'he data represents the average values from the combination of the ECE-EUDC test procedures ("combined ECErEUDC"
z~eporting method).
'Z'Al3T...L 4 HC Delta NOx Delta CO Delta 1'1VI Delta Fuel 3 0.05 -X5.8% 0.58 -13. I % 0.43 -41.8 % 0.045 -41.3 Fuel4 0.103 -12.5% 0.644 -3.4% 0.650 ,11.6% 0.076 -1.5%
Fuel s 0.118 basis 0.669 basis 0.736 basis 0.077 basis The data, revealed Significantly lower etxrissions produced from apglicants' diesel fuel blend, ~.e13, than observed with either of the conventional diesel fuels (Fuels 4 and 5). ~n particular, applicants blend, Fuel 3 produced emissions with a SS.8% decxease in hydrocarbons, 4I.8% decrease in carbon monoxide, 13.1% decrease in nitrogen oxides and 4I.3% decrease in, particulate matter as compared to the base conventional diesel fuel. However, a closer review of the data, shows that the fuels of this invention have a substantial advantage in particulates and nilrogex~ oxides emissions above that which world be expected.
See SAE 96I074 and 961075. In this regard, it is well known in the art that the most critical emissions parameter for a diesel fuel is the P1VI-NOx trade-off, i.e., there is a known inverse relationship between particulate matter and NOx. See SAE 961,074 and 961075. Thus, in regard to emissions, decreasiug one variable will normally result in increasing the other variable.
Table 5 below details the predicted changes for light duty (i.e., passenger car) diesel engines according to the well recognized ~.'uropean program on Emissions, Fuels and Engine Technologies (EPEFE) study in Europe undertaken by the government, auto and oil companies to define the relationship between ~15-fuel properties and erxiissions based on variables in density, cetane number and T95; see SAE Paper 961073, Tables 3 through 6. The left hand column indicates the two pollutants (particulate matter and nitrogen oxides) along with the changes in absolute emissions in g/,13p-hr and percent change (%
increase(positive) or % decrease(negative)) for each of the four fuel characteristics shown at the top of the columns. The emission change (in g/Hp-hr and percent) is based on a deviation of one of the four fuel characteristics as shown in parenthesis. For example, if the T95 was lowered by SS° C, the particulate emissions would decrease by 6.9% while the NOx would increase by 4.6%.
TABLE S
I7ensit~ Polyaromatics Cetane T95 (-0.027) (-7% +8 numbers) (55C) k'azticulate p..hr ,0.012 -0.003 0.003 -0.004 % -19.1.% -5.2% S.2% -6.9%
NOx g/Hp-hr 0.008 -O.O i 9 -0.001 0.026 % I.4!o -3.4% -0.2% 4.6%a Table 6 below was produced by combining the published results of Table 5, with the properties measured in. Table 3 and the emissions results of Table 4.
The resulting test data indicates the e~,Pected change ire emissions as projected by the EPEFE equations rrersus the actual changes measured during emissions testing on each of the fuels listed in Table 5, Again, all results are referenced to Puel 4 as the base fuel.
Pollutant Fuel 4 vs. S Fuel 3 vs. 5 Particulate 1''rojected -3.9% -27.7%
Actual -1.5 % -43.1 %
NOx Projected 1.2% 1.4%
Actual -3.4% -13.1 %
Fuel 4, the conventional fuel, shows very close agreement with the predictions differing by only a slight aznount with particulate emissions 2.4%
(-3.9%= 1.S%) worse than expected and N'Ox 4.b% (1.2%.: 3.4%) better than expected. For Fuel 3, the contrast from Fuel 5, the base fuel, is quite different and unexpected. In fact, applicants' diesel. fuel blend exceeded the performance predicted for particulate emissions (5S.6% above projection ~( 43.1 %_ 27.7%)/.2770 while at the same time dramatically decreasing NOx eznissions(1036% above projection [(1.4%= 1.3.1%)/.03.4). According to these projections, an improvement in particulate emissions is expected for Duel 3 and the above data not only bears this pzediction out but exceeds it. In addi~,on, the EPE>~EE predictions predict a slight increase in 1\10x. T~owever, in contrast to this prediction, the data reveals that applicants' diesel fuels resulted in a substantial reduction in the NOx emissions above the predicted value. Thus, applicants diesel fuels simultaneously result in both large NOx and particulate emissions reductions, Such results are unexpected and directly contradictory to the well recognized predictions.
rn the claims hereinafter, sulfur is to be measured by x-ray fluorescence, for example as described in ASTM D-2622; cetane is to be determined using ASTM D-613; density is to be measured by D-4052; and T95 is to be determined by ASTM D-86.
Actual -1.5 % -43.1 %
NOx Projected 1.2% 1.4%
Actual -3.4% -13.1 %
Fuel 4, the conventional fuel, shows very close agreement with the predictions differing by only a slight aznount with particulate emissions 2.4%
(-3.9%= 1.S%) worse than expected and N'Ox 4.b% (1.2%.: 3.4%) better than expected. For Fuel 3, the contrast from Fuel 5, the base fuel, is quite different and unexpected. In fact, applicants' diesel. fuel blend exceeded the performance predicted for particulate emissions (5S.6% above projection ~( 43.1 %_ 27.7%)/.2770 while at the same time dramatically decreasing NOx eznissions(1036% above projection [(1.4%= 1.3.1%)/.03.4). According to these projections, an improvement in particulate emissions is expected for Duel 3 and the above data not only bears this pzediction out but exceeds it. In addi~,on, the EPE>~EE predictions predict a slight increase in 1\10x. T~owever, in contrast to this prediction, the data reveals that applicants' diesel fuels resulted in a substantial reduction in the NOx emissions above the predicted value. Thus, applicants diesel fuels simultaneously result in both large NOx and particulate emissions reductions, Such results are unexpected and directly contradictory to the well recognized predictions.
rn the claims hereinafter, sulfur is to be measured by x-ray fluorescence, for example as described in ASTM D-2622; cetane is to be determined using ASTM D-613; density is to be measured by D-4052; and T95 is to be determined by ASTM D-86.
Claims (32)
1. A diesel fuel blend comprising a Fischer-Tropsch derived hydrocarbon distillate having a T95 0f at least 600° F, and a petroleum derived hydrocarbon distillate having a T95 no greater than 640° F
wherein the blend has a sulfur content less than 500 wppm.
wherein the blend has a sulfur content less than 500 wppm.
2. The fuel blend of claim 1 wherein the blend has an initial boiling point of at least 280° P and a T95 below about 700° F.
3. The fuel blend of claim 1 wherein the blend has an initial boiling point of at least 300° F and a T95 below about 680° F.
4. The fuel blend of claim 1 wherein the blend has an initial boiling point of at least 320° F and a T95 below about 640° F.
5. The fuel blend of claim 1 wherein the Fischer-Tropsch derived hydrocarbon distillate has an initial boiling point of at least 300° F
and a T95 of at least 650° F.
and a T95 of at least 650° F.
6. The fuel blend of claim 1 wherein the Fischer-Tropsch derived hydrocarbon distillate has an initial boiling point of at least 320° F
and a T95 of at least 700° F.
and a T95 of at least 700° F.
7. The fuel blend of claim 1 wherein the petroleum derived hydrocarbon has a T95 below 600° F.
8. The fuel blend of claim 1 wherein the blend has a sulfur content of less than 150 wppm.
9. The fuel blend of claim 1 wherein the blend has a sulfur content of less than 50 wppm.
10. The fuel blend of claim 1 wherein the blend has a sulfur content of less than 30 wppm.
11. The fuel blend of claim 1 wherein the Fischer-Tropsch distillate comprises 5-90 vol. % of the blend and the petroleum distillate comprises 90-5 vol. % of the blend.
12. The fuel blend of claim 1 wherein the Fischer-Tropsch distillate comprises 20-80 vol. % of the blend and the petroleum distillate comprises 80-20 vol. % of the blend.
13. The fuel blend of claim 1 wherein the Fischer-Tropsch distillate comprises 30-80 vol. % of the blend and the petroleum distillate comprises 80-30 vol. % of the blend.
14. The fuel blend of claim 1 wherein the blend contains less than or equal to 11 wt. % polyaromatics and a cetane number of at least 50.
15. The fuel blend of claim 14 wherein the blend contains less than or equal to 5 wt. % polyaromatics.
16. The fuel blend of claim 15 wherein the blend contains less than or equal to 1 wt. % polyaromatics.
17. The fuel blend of claim 14 wherein the blend has a density ranging from about 0.79 to about 0.85.
18. A method of producing a low sulfur fuel useful as a diesel fuel with low emissions after combustion from a petroleum derived hydrocarbon distillate having a T95 no greater than 640° F, comprising blending said petroleum distillate with a Fischer-Tropsch derived hydrocarbon distillate having a T95 of at least 600° F, wherein the Fischer-Tropsch distillate comprises 10-90 vol. % of the blend and the blend has a sulfur content of less than 500 wppm.
19. The method of claim 18 wherein the blend has a sulfur content of less than, 150 wppm.
20. The method of claim 19 wherein the blend has a sulfur content of less than 50 wppm.
21. The method of claim 20 wherein the blend has a sulfur content of less than 30 wppm.
22. The method of claim 18 wherein the blend has an initial boiling point of at least 280°F and a T95 below about 700° F.
23. The method of claim 18 wherein the blend has an initial boiling point of at least 300° F and a T95 below about 680° F.
24. The method of claim 18 wherein the blend has an initial, boiling point of at least 320° F and a T95 below about 640° F.
25. The method of claim 18 wherein the Fischer-Tropsch derived hydrocarbon distillate has an initial boiling point of at feast 300° F
and a T95 of at least 650° F.
and a T95 of at least 650° F.
26. The method of claim 18 wherein the Fischer-Tropsch derived hydrocarbon distillate has an initial boiling point of at least 320° F
and a T95 of at least 700° F.
and a T95 of at least 700° F.
27. The method of claim 18 wherein the Fischer-Tropsch distillate comprises 5-90 vol. % of the blend and the petroleum distillate comprises 90-5 vol. % of the blend.
28. The method of claim 18 wherein the Fischer-Tropsch distillate comprises 20-80 vol. % of the blend and the petroleum distillate comprises 80-20 vol. % of the blend.
29. The method of claim 18 wherein the Fischer-Tropsch distillate comprises 30-80 vol. % of the blend and the petroleum distillate comprises 80-30 vol. % of the blend.
30. The method of claim 18 wherein the blend contains less than or equal to 11 wt. % polyaromatics and a cetane number of at least 50.
31. The method of claim 30 wherein the blend contains less than or equal to 5 wt. % polyaromatics.
32. The method of claim 31 wherein the blend contains less than or equal to 1 wt. % polyaromatics.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/562,452 | 2000-05-02 | ||
| US09/562,452 US6663767B1 (en) | 2000-05-02 | 2000-05-02 | Low sulfur, low emission blends of fischer-tropsch and conventional diesel fuels |
| PCT/US2001/010857 WO2001083406A2 (en) | 2000-05-02 | 2001-04-03 | Low sulfur, low emission blends of fischer-tropsch and conventional diesel fuels |
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| CA2405780C true CA2405780C (en) | 2010-08-31 |
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| US (1) | US6663767B1 (en) |
| EP (1) | EP1303576B1 (en) |
| JP (1) | JP2004515562A (en) |
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| AU (2) | AU2001278838B2 (en) |
| BR (1) | BR0110425B1 (en) |
| CA (1) | CA2405780C (en) |
| NO (1) | NO20025258D0 (en) |
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| PT1307529E (en) * | 2000-05-02 | 2006-10-31 | Exxonmobil Res & Eng Co | F-T COMBUSTIBLE COMBINATIONS / BASE EMISSIONS BASE |
| US6833484B2 (en) * | 2001-06-15 | 2004-12-21 | Chevron U.S.A. Inc. | Inhibiting oxidation of a Fischer-Tropsch product using petroleum-derived products |
| DE60223059T2 (en) * | 2001-09-18 | 2008-07-17 | Southwest Research Institute, San Antonio | FUELS FOR HOMOGENALLY LOADED COMPACTION IGNITION MACHINES |
| US6569909B1 (en) * | 2001-10-18 | 2003-05-27 | Chervon U.S.A., Inc. | Inhibition of biological degradation in fischer-tropsch products |
| US6890423B2 (en) * | 2001-10-19 | 2005-05-10 | Chevron U.S.A. Inc. | Distillate fuel blends from Fischer Tropsch products with improved seal swell properties |
| US6863802B2 (en) | 2002-01-31 | 2005-03-08 | Chevron U.S.A. | Upgrading fischer-Tropsch and petroleum-derived naphthas and distillates |
| US7033552B2 (en) | 2002-01-31 | 2006-04-25 | Chevron U.S.A. Inc. | Upgrading Fischer-Tropsch and petroleum-derived naphthas and distillates |
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