US 6,296,757 B1Grant

Synthetic diesel fuel and process for its production

Issue Date:2001-10-02

•34 Claims

•2 Drawing Sheets

Abstract

Diesel fuels or blending stocks having excellent lubricity, oxidative stability and high cetane number are produced from non-shifting Fischer-Tropsch processes by separating the Fischer-Tropsch product into a lighter and heavier fractions, e.g., at about 700° F., subjecting the 700° F.+fraction to hydro-treating, and combining the 700° F.− portion of the hydrotreated product with the lighter fraction that has not been hydrotreated.

Metadata

Assignee

Exxon Research and Engineering Company

Inventors

Robert Jay Wittenbrink
Richard Frank Bauman
Paul Joseph Berlowitz
Bruce Randall Cook

Application Information

Application Number:US 08/544,343

Filing Date:1995-10-17

Priority Date:1995-10-17

Art Unit:7

Classifications

IPC:

C10G 1400

Field of Search:

208 27208 14208 15585 14

Patent Drawings (2 sheets)

Description

Field of the Invention

[0002] This invention relates to a distillate material having a high cetane number and useful as a diesel fuel or as a blending stock therefor, as well as the process for preparing the distillate. More particularly, this invention relates to a process for preparing distillate from a Fischer-Tropsch wax.

Background of the Invention

[0003] Clean distillates that contain no or nil sulfur, nitrogen, or aromatics, are, or will likely be in great demand as diesel fuel or in blending diesel fuel. Clean distillates having relatively high cetane number are particularly valuable. Typical petroleum derived distillates are not clean, in that they typically contain significant amounts of sulfur, nitrogen, and aromatics, and they have relatively low cetane numbers. Clean distillates can be produced from petroleum based distillates through severe hydrotreating at great expense. Such severe hydrotreating imparts relatively little improvement in cetane number and also adversely impacts the fuel's lubricity. Fuel lubricity, required for the efficient operation of fuel delivery system, can be improved by the use of costly additive packages. The production of clean, high cetane number distillates from Fischer-Tropsch waxes has been discussed in the open literature, but the processes disclosed for preparing such distillates also leave the distillate lacking in one or more important properties, e.g., lubricity. The Fischer-Tropsch distillates disclosed, therefore, require blending with other less desirable stocks or the use of costly additives. These earlier schemes disclose hydrotreating the total Fischer-Tropsch product, including the entire 700° F.− fraction. This hydro-treating results in the elimination of oxygenates from the distillate.

[0004] By virtue of this present invention small amounts of oxygenates are retained, the resulting product having both very high cetane number and high lubricity. This product is therefore useful as a diesel fuel as such, or as a blending stock for preparing diesel fuels from other lower grade material.

Summary of the Invention

[0005] In accordance with this invention, a clean distillate useful as a fuel heavier than gasoline, e.g., useful as a diesel fuel or as a diesel fuel blend stock and having a cetane number of at least about 60, preferably at least about 70, more preferably at least about 74, is produced, preferably from a Fischer-Tropsch wax and preferably derived from a cobalt or ruthenium Fischer-Tropsch catalyst, by separating the waxy product into a heavier fraction and a lighter fraction. The nominal separation is at about 700° F., and the heavier fraction contains primarily 700° F.+, and the lighter fraction contains primarily 700° F.−.

[0006] The heavier fraction is subjected to hydroisomerization in the presence of a hydroisomerization catalyst, having one or more noble or non-noble metals, at normal hydroisomerization conditions, where at least a portion of the 700° F.+ material is converted to 700° F.− material. At least a portion and preferably all of the lighter fraction, preferably after separation of C₅− (although some C₃and C₄may be dissolved in the C₅+) remains untreated, i.e., other than by physical separation, and is blended back with at least a portion and preferably all of the hydroisomerized, 700° F.−, product. From this combined product a diesel fuel or diesel blending stock in the boiling range 250° F.-700° F. can be recovered and has the properties described below.

Description of the Drawings

[0007] FIG. 1 is a schematic of a process in accordance with this invention.

[0008] FIG. 2 shows IR absorbence spectra for two fuels: I for Diesel Fuel B, and II for Diesel Fuel B with 0.0005 mmoles/gm palnitic acid (which corresponds to 15 wppm oxygen as oxygen); absorbance on the ordinate, wave length on the abscissa.

Description of Preferred Embodiments

[0009] A more detailed description of this invention may be had by referring to the drawing. Synthesis gas, hydrogen and carbon monoxide, in an appropriate ratio, contained in line 1 is fed to a Fischer-Tropsch reactor 2, preferably a slurry reactor and product is recovered in lines 3 and 4, 700° F.+ and 700° F.− respectively. The lighter fraction goes Through hot separator 6 and a 500-700° F. fraction is recovered, in line 8, while a 500° F.− fraction is recovered in line 7. The 500° F.− material goes through cold separator 9 from which C₄-gases are recovered in line 10. A C₅-500° F. fraction is recovered in line 11 and is combined with the 500-700° F. fraction in line 8. At least a portion and preferably most, more preferably essentially all of this C₅-700 fraction is blended with the hydroisomerized product in line 12.

[0010] The heavier, e.g., 700F+ fraction, in line 3 is sent to hydro-isomerization unit 5. Typical broad and preferred conditions for the hydro-isomerization process unit are shown in the table below:

[0011] While virtually any catalyst useful in hydroisomerization or selective hydrocracking may be satisfactory for this step, some catalysts perform better than others and are preferred. For example, catalysts containing a supported Group VIII noble metal, e.g., platinum or palladium, are useful as are catalysts containing one or more Group VIII base metals, e.g., nickel, cobalt, in amounts of about 0.5-20 wt %, which may or may not also include a Group VI metal, e.g., molybdenum, in amounts of about 1-20 wt %. The support for the metals can be any refractory oxide or zeolite or mixtures thereof. Preferred supports include silica, alumina, silica-alumina, silica-alumina phosphates, titania, zirconia, vanadia and other Group m, IV, VA or VI oxides, as well as Y sieves, such as ultrastable Y sieves. Preferred supports include alumina and silica-alumina where the silica concentration of the bulk support is less than about 50 wt %, preferably less than about 35 wt %.

[0012] A preferred catalyst has a surface area in the range of about 180-400 m²/gm, preferably 230-350 m²/gm, and a pore volume of 0.3 to 1.0 ml/gm, preferably 0.35 to 0.75 ml/gm, a bulk density of about 0.5-1.0 g/ml, and a side crushing strength of about 0.8 to 3.5 kg/mm.

[0013] The preferred catalysts comprise a non-noble Group VIII metal, e.g., iron, nickel, in conjunction with a Group IB metal, e.g., copper, supported on an acidic support. The support is preferably an amorphous silica-alumina where the alumina is present in amounts of less than about 30 wt %, preferably 5-30 wt %, more preferably 10-20 wt %. Also, the support may contain small amounts, e.g., 20-30 wt %o, of a binder, e.g., alumina, silica, Group IVA metal oxides, and various types of clays, magnesia, etc., preferably alumina. The catalyst is prepared by coimpregnating the metals from solutions onto the support, drying at 100-150° C., and calcining in air at 200-550° C.

[0014] The preparation of amorphous silica-alumina microspheres for supports is described in Ryland, Lloyd B., Tamele, M. W., and Wilson, J. N., Cracking Catalysts, Catalysis: volume VII, Ed. Paul H. Emmett, Reinhold Publishing Corporation, New York, 1960, pp. 5-9.

[0015] The Group VIII metal is present in amounts of about 15 wt % or less, preferably 1-12 wt %, while the Group IB metal is usually present in lesser amounts, e.g., 1:2 to about 1:20 ratio respecting the Group VIH metal. A typical catalyst is shown below:

[0016] The 700° F.+ conversion to 700° F.− in the hydroisomerization unit ranges from about 20-80%, preferably 20-50%, more preferably about 30-50%. During hydroisomerization essentially all olefins and oxygen containing materials are hydrogenated.

[0017] The hydroisomerization product is recovered in line 12 into which the C₅-700° F. stream of lines 8 and 11 are blended. The blended stream is fractionated in tower 13, from which 700° F.+ is, optionally, recycled in line 14 back to line 3, C₅− is recovered in line 16 and a clean distillate boiling in the range of 250‥700° F. is recovered in line 15. This distillate has unique properties and may be used as a diesel fuel or as a blending component for diesel fuel. Light gases may be recovered in line 16 and combined in line 17 with the light gases from the cold separator 9 and used for fuel or chemicals processing.

[0018] The diesel material recovered from the fractionator 13, has the properties shown below:

[0019] The iso paraffins are preferably mono methyl branched, and since the process utilizes Fischer-Tropsch wax, the product contains nil cyclic paraffins, e.g., no cyclohexane.

[0020] The oxygenates are contained essentially, e.g., ≧95% of the oxygenates, in the lighter fraction, e.g., the 700° F. − fraction. Further, the olefin concentration of the lighter fraction is sufficiently low as to make olefin recovery unnecessary; and flier treatment of the fraction for olefins is avoided.

[0021] The preferred Fischer-Tropsch process is one that utilizes a non-shifting (that is, no water gas shift capability) 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. Pat. No. 4,568,663 as well as European Patent 0 266 898. The hydrogen:CO ratio in the process is at least about 1.7, preferably at least about 1.75, more preferably 1.75 to 2.5.

[0022] The products of the Fischer-Tropsch process are primarily paraffinic hydrocarbons. Ruthenium produces paraffins primarily boiling in the distillate range, i.e., C₁₀-C₂₀; while cobalt catalysts generally produce more of heavier hydrocarbons, e.g., C₂₀+, and cobalt is a preferred Fischer-Tropsch catalytic metal.

[0023] Diesel fuels generally have the properties of high cetane number, usually 50 or higher, preferably at least about 60, more preferably at least about 65, lubricity, oxidative stability, and physical properties compatible with diesel pipeline specifications.

[0024] The product of this invention may be used as a diesel fuel, per se, or blended with other less desirable petroleum or hydrocarbon containing feeds of about the same boiling range. When used as a blend, the product of this invention can be used in relatively minor amounts, e.g., 10% or more, for significantly improving the final blended diesel product. Although, the product of this invention will improve almost any diesel product, it is especially desirable to blend this product with refinery diesel streams of low quality. Typical streams are raw or hydrogenated catalytic or thermally cracked distillates and gas oils.

[0025] By virtue of using the Fischer-Tropsch process, the recovered distillate has nil sulfur and nitrogen. These hereto-atom compounds are poisons for Fischer-Tropsch catalysts and are removed from the methane containing natural gas that is a convenient feed for the Fischer-Tropsch process. (Sulfur and nitrogen containing compounds are, in any event, in exceedingly low concentrations in natural gas.) Further, the process does not make aromatics, or as usually operated, virtually no aromatics are produced. Some olefins are produced since one of the proposed pathways for the production of paraffins is through an olefinic intermediate. Nevertheless, olefin concentration is usually quite low.

[0026] Oxygenated compounds including alcohols and some acids are produced during Fischer-Tropsch processing, but in at least one well known process, oxygenates and unsaturates are completely eliminated from the product by hydrotreating. See, for example, The Shell Middle Distillate Process, Eiler, J.; Posthuma, S. A.; Sie, S. T., Catalysis Letters, 1990, 7, 253-270.

[0027] We have found, however, that small amounts of oxygenates, preferably alcohols, usually concentrated in the 700° F.− fraction and preferably in the 500-700° F. fraction, more preferably in the 600-700° F. fraction, provide exceptional lubricity for diesel fuels. For example, as illustrations will show, a highly paraffinic diesel fuel with small amounts of oxygenates has excellent lubricity as shown by the BOCLE test (ball on cylinder lubricity evaluator). However, when the oxygenates were removed, for example, by extraction, absorbtion over molecular sieves, hydroprocessing, etc., to a level of less than 10 ppm wt % oxygen (water free basis) in the fraction being tested, the lubricity was quite poor.

[0028] By virtue of the processing scheme disclosed in this invention the lighter, 700° F.− fraction is not subjected to any hydrotreating. In the absence of hydrotreating of the lighter fraction, the small amount of oxygenates, primarily linear alcohols, in this fraction are preserved, while oxygenates in the heavier fraction are eliminated during the hydroisomerization step. Hydroisomerization also serves to increase the amount of iso paraffins in the distillate fuel and helps the fuel to meet pour point and cloud point specifications, although additives may be employed for these purposes.

[0029] The oxygen compounds that are believed to promote lubricity may be described as having a hydrogen bonding energy greater than the bonding energy of hydrocarbons (the energy measurements for various compounds are available in standard references); the greater the difference, the greater the lubricity effect. The oxygen compounds also have a lipophilic end and a hydrophilic end to allow wetting of the fuel.

[0030] Preferred oxygen compounds, primarily alcohols, have a relatively long chain, i.e., C₁₂+, more preferably C₁₂-C₂₄primary linear alcohols.

[0031] While acids are oxygen containing compounds, acids are corrosive and are produced in quite small amounts during Fischer-Tropsch processing at non-shift conditions. Acids are also di-oxygenates as opposed to the preferred mono-oxygenates illustrated by the linear alcohols. Thus, di or poly-oxygenates are usually undetectable by infra red measurements and are, e.g., less than about 15 wppm oxygen as oxygen.

[0032] Non-shifting Fischer-Tropsch reactions are well known to those skilled in the art and may be characterized by conditions that minimize the formations of CO₂byproducts. These conditions can be achieved by a variety of methods, including one or more of the following: operating at relatively low CO partial pressures, that is, operating at hydrogen to CO ratios of at least about 1.7/1, preferably about 1.7/1 to about 2.5/1, more preferably at least about 1.9/1, and in the range 1.9/1 to about 2.3/1, all with an alpha of at least about 0.88, preferably at least about 0.91; temperatures of about 175-225° C., preferably 180-210° C.; using catalysts comprising cobalt or ruthenium as the primary Fischer-Tropsch catalysis agent.

[0033] The amount of oxygenates present, as oxygen on a water free basis is relatively small to achieve the desired lubricity, i.e., at least about 0.001 wt % oxygen (water free basis), preferably 0.001-0.3 wt % oxygen (water free basis), more preferably 0.0025-0.3 wt %o oxygen (water free basis).

[0034] The following examples will serve to illustrate, but not limit, this invention.

[0035] Hydrogen and carbon monoxide synthesis gas (H₂:CO 2.11-2.16) were converted to heavy paraffins in a slurry Fischer-Tropsch reactor. The catalyst utilized for the Fischer-Tropsch reaction was a titania supported cobalt/rhenium catalyst previously described in U.S. Pat. No. 4,568,663. The reaction conditions were 422-428° F., 287-289 psig, and a linear velocity of 12 to 17.5 cm/sec. The alpha of the Fischer-Tropsch synthesis step was 0.92. The paraffinic Fischer-Tropsch product was then isolated in three nominally different boiling streams, separated utilizing a rough flash. The three approximate boiling fractions were: 1) the C₅-500° F. boiling fraction, designated below as F-T Cold Separator Liquids; 2) The 500-700° F. boiling fraction designated below as F-T Hot Separator Liquids; and 3) the 700° F.+ boiling fraction designated below as F-T Reactor Wax.

Example 1

[0036] Seventy wt % of a Hydroisomerized F-T Reactor Wax, 16.8 wt % Hydrotreated F-T Cold Separator Liquids and 13.2 wt % Hydrotreated F-T Hot Separator Liquids were combined and rigorously mixed. Diesel Fuel A was the 260-700° F. boiling fraction of this blend, as isolated by distillation, and was prepared as follows: The hydroisomerized F-T Reactor Wax was prepared in flow through, fixed bed unit using a cobalt and molybdenum promoted amorphous silica-alumina catalyst, as described in U.S. Pat. Nos. 5,292,989 and 5,378,348. Hydroisomerization conditions were 708° F., 750 psig H₂, 2500 SCF/B H₂, and a liquid hourly space velocity (LHSV) of 0.7-0.8. Hydroisomerization was conducted with recycle of unreacted 700° F.+reactor wax. The Combined Feed Ratio, (Fresh Feed+Recycle Feed)/Fresh Feed equaled 1.5. Hydrotreated F-T Cold and Hot Separator Liquid were prepared using a flow through fixed bed reactor and commercial massive nickel catalyst. Hydrotreating conditions were 450° F., 430 psig H₂, 1000 SCF/B H₂, and 3.0 LHSV. Fuel A is representative of a typical completely hydrotreated cobalt derived Fischer-Tropsch diesel fuel, well known in the art.

Example 2

[0037] Seventy Eight wt % of a Hydroisomerized F-T Reactor Wax, 12 wt % Unhydrotreated F-T Cold Separator Liquids, and 10 wt % F-T Hot Separator Liquids were combined and mixed. Diesel Fuel B was the 250-700° F. boiling fraction of this blend, as isolated by distillation, and was prepared as follows: The Hydroisomerized F-T Reactor Wax was prepared in flow through, fixed bed unit using a cobalt and molybdenum promoted amorphous silica-alumina catalyst, as described in U.S. Pat. Nos. 5,292,989 and 5,378,348. Hydroisomerization conditions were 690° F., 725 psig H₂, 2500 SCF/B H₂, and a liquid hourly space velocity (LHSV) of 0.6-0.7. Fuel B is a representative example of this invention.

Example 3

[0038] Diesel Fuels C and D were prepared by distilling Fuel B into two fractions. Diesel Fuel C represents the 250 to 500° F. fraction of Diesel Fuel B. Diesel Fuel D represents the 500-700° F. fraction of Diesel Fuel B.

Example 4

[0039] 100.81 grams of Diesel Fuel B was contacted with 33.11 grams of Grace Silico-aluminate zeolite: 13X, Grade 544, 8-12 mesh beads. Diesel Fuel E is the filtrated liquid resulting from this treatment This treatment effectively removes alcohols and other oxygenates from the fuel.

Example 5

[0040] Diesel Fuel F is a hydrotreated petroleum stream composed of approximately 40% cat distillate and 60% virgin distillate. It was subsequently hydrotreated in a commercial hydrotreater. The petroleum fraction has a boiling range of 250-800° F., contains 663 ppm sulfur (x-ray), and 40% FIA aromatics. Diesel Fuel F represents a petroleum base case for this invention.

Example 6

[0041] Diesel Fuel G was prepared by combining equal amounts of Diesel Fuel B with a Diesel Fuel F. Diesel Fuel G should contain 600 ppm total oxygen (neutron activation), 80 ppm 500+° F boiling primary alcohols the (GC/MS), and signal for primary alcohols indicates 320 ppm total oxygen as primary alcohols (¹H NMR; 250-700° F.). Diesel Fuel G represents an additional example for this invention where both HCS and petroleum distillates are used to comprise the diesel fuel.

Example 7

[0042] Oxygenate, dioxygenate, and alcohol composition of Diesel Fuels A, B, and E were measured using Proton Nuclear Magnetic Resonance (¹H-NMR), Infrared Spectroscopy (IR), and Gas Chromatography/Mass Spectrometry (GC/MS). ¹H-NMR experiments were done using a Brucker MSL-500 Spectrometer. Quantitative data were obtained by measuring the samples, dissolved in CDCl₃, at ambient temperature, using a frequency of 500.13 MHz, pulse width of 2.9 μs (45 degree tip angle), delay of 60 s, and 64 scans. Tetramethylsilane was used as an internal reference in each case and dioxane was used as an internal standard. Levels of primary alcohols, secondary alcohols, esters and acids were estimated directly by comparing integrals for peaks at 3.6 (2H), 3.4 (1H), 4.1 (2H) and 2.4 (2H) ppm respectively, with that of the internal standard. IR Spectroscopy was done using a Nicolet 800 spectro-meter. Samples were prepared by placing them in a KBr fixed path length cell (nominally 1.0 mm) and acquisition was done by adding 4096 scans a 0.3 cm⁻¹resolution. Levels of dioxygenates, such as carboxylic acids and esters, were measured using the absorbance at 1720 and 1738 cm⁻¹, respectively. GC/MS were performed using either a Hewlett-Packard 5980/Hewlett-Packard 5970 B Mass Selective Detector Combination (MSD) or Kratos Model MS-890 GC/MS. Selected ion monitoring of m/z 31 (CH₃O⁺) was used to quantify the primary alcohols. An external standard was made by weighing C₂-C₁₄, C₁₆and C₁₈primary alcohols into a mixture of C₈-C₁₆normal paraffins. Olefins were determined using Bromine Index, as described in ASTM D 2710. Results from these analyses are presented in Table 1. Diesel Fuel B which contains the unhydrotreated hot and cold separator liquids contains a significant amount of oxygenates as linear, primary alcohols. A significant fraction of these are the important C₁₂-C₁₈primary alcohols. It is these alcohols that impart superior performance in diesel lubricity. Hydrotreating (Diesel Fuel A) is extremely effective at removing essentially all of the oxygenates and olefins. Mole sieve treatment (Diesel Fuel E) also is effective at removing the alcohol contaminants without the use of process hydrogen. None of these fuels contain significant levels of dioxygenates, such as carboxylic acids or esters. A sample IR spectrum for Diesel Fuel B is shown in FIG. 2.

Example 8

[0043] Diesel Fuels A-G were all tested using a standard Ball on Cylinder Lubricity Evaluation (BOCLE), fuirther described as Lacey, P. I. “The U.S. Army Scuffing Load Wear Test”, Jan. 1, 1994. This test is based on ASTM D 5001. Results are reported in Table 2 as percents of Reference Fuel 2, described in Lacey.

[0044] The completely hydrotreated Diesel Fuel A, exhibits very low lubricity typical of an all paraffin diesel fuel. Diesel Fuel B, which contains a high level of oxygenates as linear, C₅-C₂₄primary alcohols, exhibits significantly superior lubricity properties. Diesel Fuel E was prepared by separating the oxygenates away from Diesel Fuel B through adsorption by 13X molecular sieves. Diesel Fuel E exhibits very poor lubricity indicating the linear C₅-C₂₄primary alcohols are responsible for the high lubricity of Diesel Fuel B. Diesel Fuels C and D represent the 250-500° F. and the 500-700° F. boiling fractions of Diesel Fuel B, respectively. Diesel Fuel C contains the linear C₅-C₁₁primary alcohols that boil below 500° F., and Diesel Fuel D contains the C₁₂-C₂₄primary alcohols that boil between 500-700° F. Diesel Fuel D exhibits superior lubricity properties compared to Diesel Fuel C, and is in fact superior in performance to Diesel Fuel B from which it is derived. This clearly indicates that the C₁₂-C₂₄primary alcohols that boil between 500-700° F. are important to producing a high lubricity saturated diesel fuel. Diesel Fuel F is representative of petroleum derived low sulfur diesel fuel, and although it exhibits reasonably high lubricity properties it is not as high as the highly paraffinic Diesel Fuel B. Diesel Fuel G is the 1:1 blend of Diesel Fuel B and Diesel Fuel F and it exhibits improved lubricity performance compared to Diesel F. This indicates that the highly paraffinic Diesel Fuel B is not only a superior neat fuel composition, but also an outstanding diesel blending component capable of improving the properties of petroleum derived low sulfur diesel fuels.

Claims

What is claimed is:

1. A material useful as a fuel heavier than gasoline or as a blending component for a distillate fuel comprising: a 250-700° F. fraction derived from a non-shifting Fischer-Tropsch catalyst process and containing

at least 95 w % paraffins with an iso to normal ratio of about 0.3 to 3.0,

<50 ppm (wt) of sulfur and nitrogen

less than about 2 wt % unsaturates, and

about 0.001 to less than 0.3 wt % oxygen on a water free basis, the oxygen being present primarily as C₁₂-C₂₄linear alcohols.

2. The material of claim 1 characterized by a cetane number of at least 70.

3. A process for producing a distillate fuel heavier than gasoline comprising:

(a) separating the product of a Fischer-Tropsch process into a heavier fraction containing 700° F.+ and a lighter fraction containing 700° F.− and C₁₂-C₂₄linear alcohols,

(b) hydroisomerizing the heavier fraction at hydroisomerization conditions and recovering a 700° F.− fraction therefrom; and

4. The process of claim 3 wherein a product boiling in the range 250-700° F. is recovered from the blended product of step (c).

5. The process of claim 4 wherein the recovered product of step (c) contains 0.001-0.3 wt % oxygen, water free basis.

6. The process of claim 4 wherein the lighter fraction is characterized by the absence of hydrotreating.

7. The process of claim 4 wherein the Fischer-Tropsch process is characterized by non-shifting conditions.

8. The product of claim 5.

9. A method for producing a distillate useful as fuel heavier than gasoline, comprising the steps of:

(a) synthesizing hydrocarbons from a gas including synthesis gas in a slurry, Fischer-Tropsch reactor using a non-shifting, cobalt catalyst under conditions producing primarily paraffinic hydrocarbons; and

(b) recovering from said hydrocarbons a 250° F. to 500° F. boiling range fraction, said fraction containing less than or equal to 50 ppm (weight) of sulfur; less than or equal to 50 ppm (weight) of nitrogen; virtually no aromatics; <2 wt % total unsaturates; and at least 0.001 wt % oxygenates as oxygen (water free basis).

10. The method of claim 9 wherein said fuel contains less than 15 ppm (weight) dioxygenates.

11. The method of claim 9 wherein the partial pressure of CO in said gas is less than 37% of the total pressure of said gas.

12. The method of claim 11 wherein said other diesel fuel material includes a hydroisomerized product of a Fisher-Tropsch process.

13. The method of claim 9 further comprising the step of combining said fraction with other heavier than gasoline diesel fuel material.

14. The method of claim 13 wherein said fuel has a cetane of at least 60.

15. The method of claim 13 wherein said fraction contains primarily paraffins having an iso to normal ratio of less than 0.3, substantially all of said iso paraffins being monomethyl branched.

16. The method of claim 13 wherein said other diesel fuel material includes a hydrotreated petroleum stream.

17. The method of claim 9 wherein said oxygenates have a hydrogen bonding energy greater than the bonding energy of hydrocarbons and a lipophilic and a hydrophilic end.

18. The method of claim 9 wherein the synthesis gas has an H₂to CO ratio of at least 1.7/1.

19. The method of claim 18 wherein the synthesizing temperature is from 175-225° C.

20. The method of claim 19 wherein alpha is at least 0.88.

21. The method of claim 9 wherein the synthesis gas has an H₂to CO ratio of between 1.7/1 and 2.5/1.

22. A heavier-than-gasoline distillate useful as fuel composition, comprising:

a 250° F. to 500° F. boiling range fraction separated from the output of a slurry Fischer-Tropsch reactor using a non-shifting, cobalt catalyst, operating with an H₂to CO ratio of at least 1.7/1 and producing primarily paraffinic hydrocarbons said fraction containing less than or equal to 50 ppm (weight) of sulfur; less than or equal to 50 ppm (weight) of nitrogen; virtually no aromatics; ≦2 wt % total unsaturates; and at least 0.001 wt % oxygenates as oxygen (water free basis).

23. The composition of claim 22 wherein said fuel contains less than 15 ppm (weight) dioxygenates.

24. The composition of claim 22 wherein the partial pressure of CO in said gas is less than 37% of the total pressure of said gas.

25. The composition of claim 24 wherein said other diesel fuel material includes a hydroisomerized product of a Fisher-Tropsch process.

26. The composition of claim 22 wherein comprising other heavier than gasoline diesel fuel material.

27. The composition of claim 22 wherein said fuel has a cetane of at least 60.

28. The composition of claim 26 wherein said fraction contains primarily paraffins having an iso to normal ratio of less than 0.3, substantially all of said iso paraffins being monomethyl branched and less than or equal to 2 wt % unsaturates.

29. The composition of claim 26 wherein said other diesel fuel material includes a hydrotreated petroleum stream.

30. The composition of claim 26 wherein said fraction contains primarily paraffins wherein said paraffins contain isoparaffins, substantially all of which being monomethyl branched, and less than equal to 2 wt % unsaturated.

31. The composition of claim 22 wherein said oxygenates have a hydrogen bonding energy greater than the bonding energy of hydrocarbons and a lipophilic and a hydrophilic end.

32. The composition of claim 22 wherein the synthesis gas has an H₂to CO ratio of between 1.7/1 and 2.5/1.

33. The composition of claim 32 wherein the synthesizing temperature is from 175-225° C.

34. The composition of claim 33 wherein the alpha is at least 0.88.

Patent Citations (260)

Patent	Date	Inventor	Cited By
US2243760	1941-05-01	Martin	Applicant
US2562980	1951-08-01	Atwell	Applicant
US2668790	1954-02-01	Good et al.	Applicant
US2668866	1954-02-01	Good et al.	Applicant
US2756183	1956-07-01	Knox, Jr.	Applicant
US2779713	1957-01-01	Cole et al.	Applicant
US2817693	1957-12-01	Koome et al.	Applicant
US2838444	1958-06-01	Teter et al.	Applicant
US2888501	1959-05-01	Folkins et al.	Applicant
US2892003	1959-06-01	Weisz	Applicant
US2906688	1959-09-01	Farmer et al.	Applicant
US2914464	1959-11-01	Burton et al.	Applicant
US2982802	1961-05-01	Folkins et al.	Applicant
US2993938	1961-07-01	Bloch et al.	Applicant
US3002827	1961-10-01	Fenske	Applicant
US3052622	1962-09-01	Johnson et al.	Applicant
US3078323	1963-02-01	Kline et al.	Applicant
US3121696	1964-02-01	Hoekstra	Applicant
US3123573	1964-03-01	Carr	Applicant
US3125511	1964-03-01	Tupman et al.	Applicant
US3147210	1964-09-01	Hass et al.	Applicant
US3206525	1965-09-01	Michaels et al.	Applicant
US3253055	1966-05-01	Goble et al.	Applicant
US3268436	1966-08-01	Arey, Jr. et al.	Applicant
US3268439	1966-08-01	Tupman et al.	Applicant
US3308052	1967-03-01	Ireland et al.	Applicant
US3338843	1967-08-01	Goble et al.	Applicant
US3340180	1967-09-01	Beuther et al.	Applicant
US3362378	1968-01-01	Borghard	Examiner
US3365390	1968-01-01	Egan et al.	Applicant
US3395981	1968-08-01	Kischio	Applicant
US3404086	1968-10-01	Plank et al.	Applicant
US3471399	1969-10-01	O'Hara	Applicant
US3486993	1969-12-01	Egan et al.	Applicant
US3487005	1969-12-01	Egan et al.	Applicant
US3507776	1970-04-01	Hann	Applicant
US3530061	1970-09-01	Orkin et al.	Applicant
US3594307	1971-07-01	Kirk, Jr.	Applicant
US3607729	1971-09-01	Robinson et al.	Applicant
US3619408	1971-11-01	Larson	Applicant
US3620960	1971-11-01	Kozlowski et al.	Applicant
US3629096	1971-12-01	Divijak, Jr.	Applicant
US3630885	1971-12-01	Egan	Applicant
US3658689	1972-04-01	Steinmetz et al.	Applicant
US3660058	1972-05-01	Feldman et al.	Applicant
US3668112	1972-06-01	Parker et al.	Applicant
US3668113	1972-06-01	Burbidge et al.	Applicant
US3674681	1972-07-01	Lyon	Applicant
US3681232	1972-08-01	Egan	Applicant
US3684695	1972-08-01	Neel et al.	Applicant
US3692695	1972-09-01	Suggitt et al.	Applicant
US3692697	1972-09-01	Kravitz et al.	Applicant
US3709817	1973-01-01	Suggitt et al.	Applicant
US3711399	1973-01-01	Estes et al.	Applicant
US3717586	1973-02-01	Suggitt et al.	Applicant
US3725302	1973-04-01	Shimely	Applicant
US3761388	1973-09-01	Bryson et al.	Applicant
US3767562	1973-10-01	Sze et al.	Applicant
US3770618	1973-11-01	Adams	Applicant
US3775291	1973-11-01	Sze	Applicant
US3794580	1974-02-01	Ladeur	Applicant
US3814682	1974-06-01	Christman et al.	Applicant
US3830723	1974-08-01	Ladeur et al.	Applicant
US3830728	1974-08-01	Mounce	Applicant
US3840508	1974-10-01	Ballard et al.	Applicant
US3840614	1974-10-01	Kravitz et al.	Applicant
US3843509	1974-10-01	Suto et al.	Applicant
US3843746	1974-10-01	Kravitz et al.	Applicant
US3848018	1974-11-01	Robson	Applicant
US3852186	1974-12-01	Christman et al.	Applicant
US3852207	1974-12-01	Stangeland et al.	Applicant
US3861005	1975-01-01	Steinmetz et al.	Applicant
US3864425	1975-02-01	Gardner	Applicant
US3870622	1975-03-01	Ashton et al.	Applicant
US3876522	1975-04-01	Campbell et al.	Applicant
US3887455	1975-06-01	Hamner	Applicant
US3915843	1975-10-01	Franck et al.	Applicant
US3963601	1976-06-01	Hilfman	Applicant
US3976560	1976-08-01	Erickson	Applicant
US3977961	1976-08-01	Hamner	Applicant
US3977962	1976-08-01	Arey, Jr. et al.	Applicant
US3979279	1976-09-01	Yan	Applicant
US4014821	1977-03-01	Hamner	Applicant
US4032304	1977-06-01	Dorer, Jr. et al.	Applicant
US4032474	1977-06-01	Goudriaan et al.	Applicant
US4041095	1977-08-01	Kuo	Applicant
US4051021	1977-09-01	Hamner	Applicant
US4059648	1977-11-01	Derr et al.	Applicant
US4067797	1978-01-01	Chen	Applicant
US4073718	1978-02-01	Hamner	Applicant
US4087349	1978-05-01	Baird, Jr.	Applicant
US4125566	1978-11-01	Dinh	Applicant
US4139494	1979-02-01	Itoh et al.	Applicant
US4162962	1979-07-01	Stangeland	Applicant
US4186078	1980-01-01	Itoh et al.	Applicant
US4212771	1980-07-01	Hamner	Applicant
US4263127	1981-04-01	Rausch et al.	Applicant
US4304871	1981-12-01	Brennan et al.	Applicant
US4342641	1982-08-01	Reif et al.	Applicant
US4378973	1983-04-01	Sweeney	Applicant
US4390414	1983-06-01	Cody	Applicant
US4394251	1983-07-01	Miller	Applicant
US4427534	1984-01-01	Brunn et al.	Applicant
US4427791	1984-01-01	Miale	Applicant
US4428819	1984-01-01	Shu et al.	Applicant
US4444895	1984-04-01	Fung et al.	Applicant
US4451572	1984-05-01	Cody	Applicant
US4472529	1984-09-01	Johnson et al.	Applicant
US4477586	1984-10-01	McDaniel	Applicant
US4518395	1985-05-01	Petronella	Applicant
US4527995	1985-07-01	Itow et al.	Applicant
US4529526	1985-07-01	Inoue et al.	Applicant
US4539014	1985-09-01	Sweeney	Applicant
US4568663	1986-02-01	Mauldin	Applicant
US4579986	1986-04-01	Sie	Applicant
US4588701	1986-05-01	Chiang	Applicant
US4594172	1986-06-01	Sie	Applicant
US4599162	1986-07-01	Yen	Applicant
US4608151	1986-08-01	Miller	Applicant
US4618412	1986-10-01	Hudson et al.	Applicant
US4627908	1986-12-01	Miller	Applicant
US4645585	1987-02-01	White	Examiner
US4673487	1987-06-01	Miller	Applicant
US4684756	1987-08-01	Derr, Jr. et al.	Applicant
US4695365	1987-09-01	Ackelson	Applicant
US4755280	1988-07-01	Hudson et al.	Applicant
US4764266	1988-08-01	Chen et al.	Applicant
US4804802	1989-02-01	Evans	Applicant
US4832819	1989-05-01	Hamner	Applicant
US4851109	1989-07-01	Chen et al.	Examiner
US4855530	1989-08-01	LaPierre et al.	Applicant
US4875992	1989-10-01	Hamner	Applicant
US4900707	1990-02-01	Cody et al.	Applicant
US4906599	1990-03-01	Cody et al.	Applicant
US4911821	1990-03-01	Katzer et al.	Applicant
US4914786	1990-04-01	Hamnet et al.	Examiner
US4919786	1990-04-01	Hamner	Applicant
US4919788	1990-04-01	Chen et al.	Applicant
US4923841	1990-05-01	Hamner	Applicant
US4929795	1990-05-01	Cody et al.	Applicant
US4937399	1990-06-01	Wachter et al.	Applicant
US4943672	1990-07-01	Hamner	Applicant
US4959337	1990-09-01	Cody et al.	Applicant
US4960504	1990-10-01	Pellet	Applicant
US4962269	1990-10-01	LaPierre et al.	Applicant
US4982031	1991-01-01	Chen	Applicant
US4990713	1991-02-01	Le et al.	Applicant
US4992159	1991-02-01	Cody	Applicant
US4992406	1991-02-01	Mauldin	Applicant
US5037528	1991-08-01	Garwood et al.	Applicant
US5059299	1991-10-01	Cody	Applicant
US5059741	1991-10-01	Foley	Applicant
US5110445	1992-05-01	Chen et al.	Applicant
US5156114	1992-10-01	Gunnerman	Applicant
US5157187	1992-10-01	Le et al.	Applicant
US5158671	1992-10-01	Cody et al.	Applicant
US5183556	1993-02-01	Reilly et al.	Applicant
US5187138	1993-02-01	Davis	Applicant
US5281347	1994-01-01	Igarashi et al.	Applicant
US5282958	1994-02-01	Santilli et al.	Applicant
US5292988	1994-03-01	Wu	Applicant
US5292989	1994-03-01	Davis	Applicant
US5302279	1994-04-01	Degnan et al.	Applicant
US5306860	1994-04-01	Bigeard et al.	Applicant
US5308365	1994-05-01	Kesling	Applicant
US5324335	1994-06-01	Benham	Applicant
US5345019	1994-09-01	Bigeard et al.	Applicant
US5348982	1994-09-01	Herbolzheimer et al.	Applicant
US5362378	1994-11-01	Borghard et al.	Applicant
US5370788	1994-12-01	Dai	Applicant
US5378249	1995-01-01	Morrison	Applicant
US5378348	1995-01-01	Davis et al.	Applicant
US5378351	1995-01-01	Guichard et al.	Applicant
US5385588	1995-01-01	Brennan	Applicant
US5479775	1996-01-01	Kraemer et al.	Applicant
US5500449	1996-03-01	Benham et al.	Applicant
US5504118	1996-04-01	Benham et al.	Applicant
US5506272	1996-04-01	Benham et al.	Applicant
US5522983	1996-06-01	Cash et al.	Applicant
US5538522	1996-07-01	Ahmed	Applicant
US5543437	1996-08-01	Benham et al.	Applicant
US5545674	1996-08-01	Behrmann et al.	Applicant
US5689031	1997-11-01	Berlowitz et al.	Examiner
US5766274	1998-06-01	Winttenbrink et al.	Examiner
US5807413	1998-09-01	Wittenbrink et al.	Examiner
AU275062	1964-07-01		Applicant
CA539698	1957-04-01		Applicant
CA700237	1964-12-01		Applicant
CA954058	1974-09-01		Applicant
DE2251156	1973-04-01		Applicant
DE3030998	1982-04-01		Applicant
DEP3030998.9	1982-04-01		Applicant
EP113045A1	1984-07-01		Applicant
EP153782	1985-09-01		Applicant
EP227218A1	1987-07-01		Applicant
EP266898A2	1988-05-01		Applicant
EP281992A3	1988-09-01		Applicant
EP323092	1988-12-01		Applicant
EP321301A3	1989-06-01		Applicant
EP418860A1	1991-03-01		Applicant
EP374461B1	1992-05-01		Applicant
EP515256A1	1992-11-01		Applicant
EP515270A1	1992-11-01		Applicant
EP532118	1993-03-01		Applicant
EP532117	1993-03-01		Applicant
EP532117A1	1993-03-01		Applicant
EP441014B1	1993-04-01		Applicant
EP542528A1	1993-05-01		Applicant
EP555006A1	1993-08-01		Applicant
EP566348A	1993-10-01		Applicant
EP566348A2	1993-10-01		Applicant
EP587246	1994-03-01		Applicant
EP587245A1	1994-03-01		Applicant
EP634472A1	1995-01-01		Applicant
EP668342A1	1995-08-01		Applicant
EP460957B1	1995-08-01		Applicant
EP753563A1	1997-01-01		Applicant
EP569228B1	1998-06-01		Applicant
FR732964	1932-03-01		Applicant
FR859686	1939-08-01		Applicant
FR2137490	1972-04-01		Applicant
FR2650289	1991-02-01		Applicant
GB728543	1955-04-01		Applicant
GB823010	1959-11-01		Applicant
GB848198	1960-09-01		Applicant
GB953188	1964-03-01		Applicant
GB951997	1964-03-01		Applicant
GB953189	1964-03-01		Applicant
GB1065205	1967-04-01		Applicant
GB1306646	1973-02-01		Applicant
GB1342499	1974-01-01		Applicant
GB1342500	1974-01-01		Applicant
GB1381004	1975-01-01		Applicant
GB1440230	1976-06-01		Applicant
GB1460476	1977-01-01		Applicant
GB1493928	1977-11-01		Applicant
GB1499570	1978-02-01		Applicant
JP7310096	1919-05-01		Applicant
JP6200262	1929-07-01		Applicant
JP49035323	1974-04-01		Applicant
JP2302561	1990-12-01		Applicant
JPH3-231990	1991-10-01		Applicant
JP2302561	1991-10-01		Applicant
WO92/02601	1992-02-01		Applicant
WO92/01769	1992-02-01		Applicant
WO92/14804	1992-09-01		Applicant
WO94/17160	1994-08-01		Applicant
WO94/20593	1994-09-01		Applicant
WO94/28095	1994-12-01		Applicant
WO95/02695	1995-01-01		Applicant
WO95/03377	1995-02-01		Applicant
WO95/06695	1995-03-01		Applicant
WO95/27021	1995-10-01		Applicant
WO96/23855	1996-08-01		Applicant
WO96/26996	1996-09-01		Applicant
WO97/03750	1997-02-01		Applicant
WO97/04044	1997-02-01		Applicant
WO97/14768	1997-04-01		Applicant
WO97/14769	1997-04-01		Applicant
WO97/21787	1997-06-01		Applicant

Non-Patent Literature (51)

Ward, “Compos. of F-T Diesel Fuel”, Div. Pet. Chem. 117th Mtg. ACS (1950).Applicant
Morgan et al, “Some Comparative Chemical, Physical and Compatibility Properties of Sasol Slurry Phase Distillate Diesel Fuel”, SAE No. 982488 (1998), pp. 1-9.Applicant
Agee, “A New Horizon For Synthetic Fuels”, World Conference on Transportation Fuel Quality Oct. 6-8, 1996.Applicant
Norton et al, “Emissions from Trucks using Fischer-Tropsch Diesel Fuel”, SAE No. 982526, pp. 1-10 (1998).Applicant
Booth et al (Shell) “Severe hydrotreating of diesel can cause fuel-injector pump failure”, PennWell Publishing Company, Oil & Gas Journal (Aug. 16, 1993).Applicant
The Clean Fuels Reports, “Volvo Demonstrates Benefits of Reformulated Diesel” “Research and Technology”, pp. 166-170, Sep. 1995.Applicant
The Clean Fuels Report, “Cetane Number is Major Control for Diesel Emissions with Catalyst”, pp. 170-173, Sep. 1995.Applicant
Signer et al, “European Programme on Emissions, Fuels and Engine Technologies (EPEFE)—Heavy Duty Diesel Study”, SAE No 961074, pp. 1-21, International Sprin Guels & Lubricants Meetings, Michigan, May 6-8, 1996.Applicant
Erwin et al, “The Standing of Fischer-Tropsch Diesel in an Assay of Fuel Performance and Emissions”, Southwest Research Institute, Contract No. NREL SUB YZ-2-113215-1 (Oct. 26, 1993).Applicant
M'Hamdi et al, “Packed Column SFC of Gas Oils”, J. High Resol. Chromatogr., vol. 21, pp. 94-102 (Feb. 1998).Applicant
Fraile et al, “Experimental Design Optimization of the Separation of the Aromatic Compounds in Petroleum Cuts by Supercricial Fluid Chromatography”, Journal of High Resolution Chromatography, vol. 16, pp. 169-174 (Mar. 1993).Applicant
Andersson et al, “Characterization of fuels by multi-dimensional supercritical fluid chromatography and supercritical fluid chromatography-mass spectrometry”, Journal of Chromatography, 641, pp. 347-355 (1993).Applicant
Di Sanzo et al, “Determination of Aromatics in Jet and Diesel Fuels by Supercritical Fluid Chromatography with Flame Ionization Detection (SFC-FID): A Quantitative Study”, Journal of Chromatographic Science, vol. 29, Jan. 1991.Applicant
Lee et al, “Development of Supercritical Fluid Chromatographic Method for Determination of Aromatics in Heating Oils and Diesel Fuels”, Energy & Fuels, 3, pp. 80-84 (1989), American Chemical Society.Applicant
T. L. Ullman, “Effects of Cetane Number, Cetane Improver, Aromatics, Aromatics, and Oxygenates on 1994 Heavy-Duty Diesel Engine Emissions”, SAE Paper 941020.Applicant
K. B. Spreen, “Effects of Cetane Number, Aromatics, and Oxygenates on Emissions From a 1994 Heavy-Duty Diesel Engine With Exhaust Catalyst”, SAE Paper 950250.Applicant
T. L. Ullman, “Effects of Cetane Number on Emissions From a Prototype 1998 Heavy-Duty Diesel Engine”, SAE Paper 950251.Applicant
J. S. Freely, “Abatement of NOx from Diesel Engines: Status & Technical Challenges”, SAE Paper 950747.Applicant
J. Leyer, “Design Aspects of Lean NOx Catalysts for Gasoline & Diesel Applications”, SAE Paper 952495.Applicant
M. Kawanami, “Advanced Catalyst Studies of Diesel NOx Reduction for On-Highway Trucks”, SAE Paper 950154.Applicant
Anderson, “Det. of Ox and Olefin Compd Types by IR . . . ”, Analyt. Chem., vol. 20, No. 11 (Nov. 1946), pp. 998-1006.Applicant
Bruner, “Syn. Gasoline From Nat. Gas”, Ind. & Eng. Chem., vol. 41, No. 11 (1948), pp. 2511-2515.Applicant
Bryant, “Impr. Hydroxylamine Meth. for Det. Aldeh. & Ketones . . . ”, p. 57 (Jan. 1935).Applicant
DuBois, “Det. of Bromine Addition Numbers”, Analyt. Chem., vol. 20, No. 7, pp. 624-627 (1948).Applicant
Friedel, “Compos. of Synth. Liquid Fuels. I . . . ”, JACS 72, pp. 1212-1215 (1950).Applicant
Johnston, “Det. of Olefins in Gasoline”, Analyt. Chem. 805-812 (1947).Applicant
Niederl, “Micromethods of Quantitative Organic Analysis”, pp. 263-272, 2nd ed. (J. Wiley & Sons, NY 1942).Applicant
Puckett, “Ignition Qualities of HC in the Diesel Fuel Boiling Range” in Information Circular Bureau of Mines 7474 (Jul. 1948).Applicant
Smith, “Rapid Det. of Hydroxyl . . . ”, p. 61 (Jan. 1935).Applicant
Tilton, “Prod. of High Cetane Number Diesel Fuels by Hydrogenation”, Ind. & Eng. Chemistry, vol. 40, pp. 1270-1279 (Jul. 1948).Applicant
Underwood, “Industrial Synthesis of HC from Hydrogen and Carbon Monoxide”, Ind. & Eng. Chemistry, vol. 32, No. 4, pp. 450-454.Applicant
Ward, “Superfractionation Studies”, Ind. & Eng. Chem. vol. 39, pp. 105-109 (109th ACS meeting).Applicant
Wheeler, “Peroxide Formation as a Meas. of Autoxidative Determination”, Oil & Soap 7, 87 (1936).Applicant
Eiler, “Shell Middle Dist.” Cat. Letters 7, 253-270 (1990).Applicant
Lanh, J. Cat., 129, 58-66 (1991). Convers. of Cyclohexane . . .Applicant
Rappold, “Industry pushes use of PDC bits . . . ”, J. Oil & Gas, Aug. 14, 1995.Applicant
Shah et al, USDOE/USDOC NTIS, UOP, Inc., Fischer-Tropsch Wax Characterization and Upgrading—Final Report, DE 88-014638, Jun. 1988 (“UOP Report”).Applicant
Signer, The Clean Fuels Report, “Southwest Research Institute Study Delineates The Effects of Diesel Fuel Composition on Emissions”, pp. 153-158 (Jun. 1995).Applicant
Lacy, “The U.S. Army Scuffing Load Wear Test”, Jan. 1, 1994.Applicant
Ryland et al, “Cracking Catalyst”, Catalysis vol. VII, P. Emmett, ed., Reinhold Publ. NY (1960), pp. 5-9.Applicant
Stournas, “Eff. of Fatty Acids . . . ”, JAOC 72 (4) (1995).Applicant
SwRI Gear Oil Scuff Test (GOST) Flyer, Gear Oil Scuff Test (GOST), 2197.Applicant
Lacey, Paul I., “Wear Mechanism Evaluation and Measurement in Fuel-Lubricated Components”, Sep. 1994.Applicant
W. Li et al, “Group-Type Separation of Diesel Fuels Using Packed Capillary Column Supercritical Fluid Chromatography” Anal. Chem., 1995, 67, 647-654.Applicant
Jimell Erwin, “Assay of Diesel Fuel Components Properties and Performance”, ACS Symposium on Processing & Selectivity of Synthetic Fuels, pp. 1915-1923, Aug. 23-28, 1992.Applicant
P. Anderson et al, “Quantitative hydrocarbon group analysis of gasoline and diesel fuel by supercritical fluid chromatography”, Journal of Chromatography, 595 (1992), pp. 301-311.Applicant
S. Win Lee, “Initial Validation of a New Procedure for Determining Aromatics in Petroleum Distillates”, Journal of Liquid Chromatography, 13(16), pp. 3211-3227, (1990).Applicant
B. J. Fuhr et al, “Determination of Aromatic Types in Middle Distillates by Supercritical Fluid Chromatography”, LC-GC, vol. 8, No. 10, pp. 800-804 (1990).Applicant
S. Win Lee, “Investigation of Methods for Determining Aromatic Structural Component Information in Middle Distillate Fuels”, 196th ACS Nat'l Meet, ACS Div. Fuel Chem. Prepr., vol. 33, No. 4, pp. 883-980 (1988).Applicant
P. Sohar, “Nuclear Magnetic Resonance Spectroscopy”, vol. II, pp. 92-102, CRC Press (1983).Applicant
Alan Goldup et al, “Determination of Trace Quantities of Water in Hydrocarbons”, Analytical Chemistry, vol. 38, No. 12, pp. 1657-1661, Nov. 1996.Applicant

Abstract