AU730173B2 - Synthetic diesel fuel and process for its production - Google Patents

Description

rUuIU I I 21591 Regulaton 3.2(2)

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT 4**e 9* Application Number: Lodged: Invention Title: SYNTHETIC DIESEL FUEL AND PROCESS FOR ITS PRODUCTION The following statement Is a full description of this Invention, Including the best method of performing It known to -us SYNTHETIC DIESEL FUEL AND PROCESS FOR ITS PRODUCTION RELATED APPLICATION This application is a divisional of Australian Patent Application No. 73951/96 filed 8 th October, 1996.

FIELD OF THE INVENTION The invention relates to a process for producing a distillate fuel heavier than gasoline. More particularly, this invention relates to a process for preparing distillate from a Fischer-Tropsch process product, particularly wax.

BACKGROUND OF THE INVENTION 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 20 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, 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 371 0 C- fraction. This hydrotreating result in the elimination of oxygenates from the distillate.

By virtue of this present invention small amount 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.

2 SUMMARY OF THE INVENTION The broadest aspect of this invention provides a process for producing a distillate fuel material heavier than gasoline including: separating the product of a Fischer-Tropsch process into a heavier fraction and a lighter fraction; hydroisomerizing the heavier fraction at hydroisomerization conditions and recovering a 3710C- fraction therefrom; and blending at least a portion of the recovered fraction of step with at least a portion of the lighter fraction.

10 In accordance with this invention, a distillate useful as a fuel heavier than gasoline, useful as a diesel fuel or as a diesel fuel blend stock and having a high cetane number advantageously of at least about 60, preferably at least about 70, more preferably at least about 74, is produced preferably from a Fischer-Topsch wax and preferably derived from a cobalt or ruthenium Fischer-Tropsch catalyst, by 15 separating the waxy product into a heavier fraction and a lighter fraction. The nominal separation is at about 371°C, and the heavier fraction contains primarily 3710C+, and the lighter fraction contains primarily 3710C-.

The heavier fraction is subjected to hydroisomerization in the presence of a hydroisomerization catalyst, having one or more noble or non-noble metals, at 20 normal hydroisomerization conditions, where at least a portion of the 3710C+ material is converted to 3710C- material. At least a portion and preferably all of the lighter fraction, preferably after separation of Cs- (although some C3 and C4 may be dissolved in the Cs+) remains untreated, other than by physical separation, and is blended back with at least a portion and preferably all of the hydroisomerized, 3710C- product. From this combined product a diesel fuel or diesel blending stock in the boiling range 1210C-3710C can be recovered and has the properties described below.

DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic of a process in accordance with this invention.

Figure 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); absorbence on the ordinate, wave length of the abscissa.

DESCRIPTION OF PREFERRED EMBODIMENTS 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, 371 0 C+ and 371 0 C- respectively. The lighter fraction goes through hot separator 6 and a 260-371 0 C fraction is recovered, in line 8, while a 260°C-fraction is recovered in line 7. The 260 0 C-material goes through cold separator 9 from which C 4 gases are recovered in line 10. A C 5 -260 0 C fraction is recovered in line 11 and is combined with the 260-371 0 C fraction in line 8. At least a portion and preferably most, more preferably essentially all of this C 5 -371°C fraction is blended with the hydroisomerized product in line 12.

The heavier, 371 0 C+ fraction, in line 3 is sent to hydroisomerization unit 5. Typical broad and preferred conditions for the hydroisomerization process unit are shown in the table below: Condition Broad Range Preferred Range Temperature, °C 149-427 287-399 Total Pressure, bar 0-172 20-82.5 Hydrogen Treat Rate, NL/L 89-890 356-712 Hydrogen Consumption Rate, NL/L 8.9-89 17.8-53.4 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, platinum or palladium, are useful as are catalysts containing one or more Group VIII base metals, nickel, cobalt, in amounts of about 0.5-20 wt%, which may or may not also include a Group VI metal, molybdenum, in amounts of about 1-20 wt/o. 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 III, IV, VA or VI oxides, as well as Y sieves, such as ultrastable Y sieves. Preferred supports include alumina and -4silica-alumina where the silica concentration of the bulk support is less than about 50 wt%, preferably less than about 35 wt'/o%.

A preferred catalyst has a surface area in the range of about 180-400 m 2 /gm, preferably 230-350 m 2 /gmn, and a pore volume of 0.3 to 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.

The preferred catalysts comprise a non-noble Group VIII metal, iron, nickel, in conjunction with a Group IB metal, 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 *30 wt%/o, more preferably 10-20 wt%/o. Also, the support may contain small amounts, 20-30 wt%/o, of a binder, 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.

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

The Group VIE metal is present in amounts of about 15 wt% or less, preferably 1-12 wt%/o, while the Group IB metal is usually present in lesser amounts, 1:2 to about 1:20 ratio respecting the Group VIII metal. A typical catalyst is shown below: Ni, wt/o 2.5-3.5 Cu, wto 0.25-0.35 A1203-SiO2 65-75 A1 2 0 3 (binder) 25-30 Surface Area 290-355 m 2 /gm Pour Volume (Hg) 0.35-0.45 ml/gm Bulk Density 0.58-0.68 g/ml The 371 0 C+ conversion to 371 0 C- in the hydroisomerization unit ranges from about 20-80%, preferably 20-50%, more preferably about 30-50%.

During hydroisomerization essentially all olefms and oxygen containing materials are hydrogenated.

The hydroisomerization product is recovered in line 12 into which the C 5 -371°C stream of lines 8 and 11 are blended. The blended stream is fractionated in tower 13, from which 371 0 C+ is, optionally, recycled in line 14 back to line 3, C 5 is recovered in line 16 and a clean distillate boiling in the range of 121-371 0 C 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.

The diesel material recovered from the fractionator 13, has the S properties shown below: paraffins at least 95 preferably at least 96 more preferably at least 97 still more preferably at least 98 wt/o, and most preferably at least 99 wt/%; iso/normal ratio about 0.3 to 3.0, preferably 0.7-2.0; sulfur 50 ppm preferably nil; nitrogen 50 ppm preferably 5 20 ppm, more preferably nil; unsaturates 2 wt/o; (olefins and aromatics) oxygenates about 0.001 to less than 0.3 wt%/ oxygen water-free basis.

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

-6- The oxygenates are contained essentially, 95% of the oxygenates, in the lighter fraction, the 371°C- fraction. Further, the olefin concentration of the lighter fraction is sufficiently low as to make olefin recovery unnecessary; and further treatment of the fraction for olefins is avoided.

The preferred Fischer-Tropsch process is one that utilizes a nonshifting (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. Patent 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 The products of the Fischer-Tropsch process are primarily paraffinic hydrocarbons. Ruthenium produces paraffins primarily boiling in the distillate range, C 10

-C

20 while cobalt catalysts generally produce more of heavier hydrocarbons, C 2 0 and cobalt is a preferred Fischer-Tropsch catalytic metal.

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

The product of the process of the 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, 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.

-7- 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 olefmic intermediate. Nevertheless, olefin concentration is usually quite low.

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, Posthuma, Sie, Catalysis Letters, 1990, 7, 253-270.

We have found, however, that small amounts of oxygenates, preferably alcohols, usually concentrated in the 371 0 C- fraction and preferably in the 260-371 0 C fraction, more preferably in the 315-371 0 C fraction, provide exceptional lubricity for diesel fuels. For example, as illustrations will show, a highly paraffiic 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 ppm wt%/ oxygen (water free basis) in the fraction being tested, the lubricity was quite poor.

By virtue of the processing scheme disclosed in this invention the lighter, 371 0 C- 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 ofiso 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.

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.

Preferred oxygen compounds, primarily alcohols, have a relatively long chain, C 12 more preferably C 12 -C24 primary linear alcohols.

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, less than about -15 wppm oxygen as oxygen.

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 CO 2 byproducts. 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 0 C, preferably 180-210 0 C; using catalysts comprising cobalt or ruthenium as the primary Fischer-Tropsch catalysis agent.

The amount of oxygenates present, as oxygen on a water free basis is relatively small to achieve the desired lubricity, 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%/ oxygen (water free basis).

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

-9- Hydrogen and carbon monoxide synthesis gas (H 2 :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 US Patent 4,568,663. The reaction conditions were 216-220 0 C, 19.7-19.9 BAR, 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 C 5 -260 0 C boiling fraction, designated below as F-T Cold Separator Liquids; 2) The 260-371 0 C boiling fraction designated below as F-T Hot Separator Liquids; and 3) the 371 0 C+ boiling fraction designated below as F-T Reactor Wax.

EXAMPLE 1 Seventy wt%/ of a Hydroisomerized F-T Reactor Wax, 16.8 wt%/ Hydrotreated F-T Cold Separator Liquids and 13.2 wt/o Hydrotreated F-T Hot Separator Liquids were combined and rigorously mixed. Diesel Fuel A was the 126-37 1C 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 US Patent 5,292,989 and US Patent 5,378,348. Hydroisomerization conditions were 375 0 C, 51.5 bar H 2 445 NL/L SCF/B H 2 and a liquid hourly space velocity (LHSV) of 0.7-0.8.

Hydroisomerization was conducted with recycle of unreacted 3710C+ 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 2320C, 29.5 bar H 2 178 NL/L H 2 and LHSV. Fuel A is representative of a typical completely hydrotreated cobalt derived Fischer-Tropsch diesel fuel, well known in the art.

EXAMPLE 2 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 121-371°C 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 silicaalumina catalyst, as described in US Patent 5,292,989 and US Patent 5,378,348.

Hydroisomerization conditions were 365 0 C, 49.8 bar H 2 445 NL/L H 2 and a liquid hourly space velocity (LHSV) of 0.6-0.7. Fuel B is a representative example of this invention.

EXAMPLE 3 Diesel Fuels C and D were prepared by distilling Fuel B into two Sfractions. Diesel Fuel C represents the 121-260°C fraction of Diesel Fuel B.

Diesel Fuel D represents the 260-3710C fraction of Diesel Fuel B.

EXAMPLE 4 100.81 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 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 121-426 0 C, contains 663 ppm sulfur (x-ray), and 40% FIA aromatics.

Diesel Fuel F represents a petroleum base case for this invention.

-11- EXAMPLE 6 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 260°C+ boiling primary alcohols the (GC/MS), and signal for primary alcohols indicates 320 ppm total oxygen as primary alcohols (1H NMR; 121-371 0 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 *Oxygenate, dioxygenate, and alcohol composition of Diesel Fuels A, B, and E were measured using Proton Nuclear Magnetic Resonance 1

H-

NMR), Infrared Spectroscopy and Gas Chromatography/Mass Spectrometry (GC/MS). 1 H-NMR experiments were done using a Brucker MSL-500 Spectrometer. Quantitative data were obtained by measuring the samples, dissolved in CDC1 3 at ambient temperature, using a frequency of 500.13 MHz, pulse width of 2.9 pts (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 3.4 4.1 (2H) and 2.4 (2H) ppm respectively, with that of the internal standard. IR Spectroscopy was done using a Nicolet 800 spectrometer. 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- 1 resolution. 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 5970B Mass Selective Detector Combination (MSD) or Kratos Model MS-890 GC/MS.

Selected ion monitoring of m/z 31 (CH 3 O was used to quantify the primary alcohols. An external standard was made by weighing C 2

-C

14

C

16 and C 18 primary alcohols into a mixture of C 8

-C

16 normal paraffins. Olefms 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 -12oxygenates as linear, primary alcohols. A significant fraction of these are the important C 12

-C

18 primary 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 Figure 2.

TABLE 1 Oxygenate, and dioxygenate (carboxylic acids, esters) composition of All Hydrotreated Diesel Fuel (Diesel Fuel Partially :Hydrotreated Diesel Fuel (Diesel Fuel and the Mole Sieve Treated, Partially Hydrotreated Diesel Fuel (Diesel Fuel E).

9* *o 9 Diesel Diesel Diesel Fuel A Fuel B Fuel E wppm Oxygen in dioxygenates, None None None (carboxylic acids, esters) (IR) Detected Detected Detected wppm Oxygen in C 5

-C

1 8 None 640 ppm None primary alcohols (1H NMR) Detected Detected wppm Oxygen in C 5

-C

1 8 5.3 824 None primary alcohols (GC/MS) Defected wppm Oxygen in C 12 -C1 8 3.3 195 ppm None primary alcohols (GC/MS) Detected Total Olefins mmol/g (Bromine 0.004 0.78 Index, ASTM D 2710) EXAMPLE 8 Diesel Fuels A-G were all tested using a standard Ball on Cylinder Lubricity Evaluation (BOCLE), further described as Lacey, P. I. "The U.S. Army 13- Scuffing Load Wear Test", January 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.

TABLE 2 BOCLE results for Fuels A-G. Results reported as percents of Reference Fuel 2 as described in Diesel Fuel Reference Fuel 2 A 42.1 B 88.9 C 44.7 D 94.7 E 30.6 F 80.0 G 84.4 ee* 0. 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, C 5

-C

24 primary 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

C

5

-C

2 4 primary alcohols are responsible for the high lubricity of Diesel Fuel B.

Diesel Fuels C and D represent the 121-260 0 C and the 260-371 0 C boiling fractions of Diesel Fuel B, respectively. Diesel Fuel C contains the linear C 5

C

1 1 primary alcohols that boil below 260 0 C, and Diesel Fuel D contains the

C

12

-C

24 primary alcohols that boil between 260-371 0 C. 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 C 12

-C

2 4 primary alcohols that boil between 260-371 0 C 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 14high 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.

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S*

S e *e e

Claims (11)

1. A process for producing a distillate fuel material heavier than gasoline including: separating the product of a Fischer-Tropsch process into a heavier fraction and a lighter fraction containing C12+ alcohols; hydroisomerizing the heavier fraction at hydroisomerization conditions and recovering a 371 0 C- fraction therefrom; and blending at least a portion of the recovered fraction of step with at least a portion of the lighter fraction.

2. The process of claim 1 wherein a product boiling in the range 121-3710C is recovered from the blended product of step

3. The process of claim 2 wherein the recovered product of step contains 0.001-0.3 wt% oxygen, water free basis.

4. The process of claim 2 wherein the lighter fraction is characterized by the absence of hydrotreating. *o

5. The process of claim 5 wherein the lighter fraction contains essentially all of the C12-C24 primary alcohols.

6. The process of claim 2 wherein the Fischer-Tropsch process is characterized by non-shifting conditions.

7. The process of claim 7 wherein. the Fischer-Tropsch process is further characterized by using a cobalt containing catalyst.

8. The process of claims 7 or 8 wherein said Fischer-Tropsch process is further characterized as being carried out in a slurry. 16

9. The process of any one of claims 1, 2 and 4 to 9 further characterized in that the product is at least 95 wt% paraffins with an iso to normal ratio of 0.3 to 50 ppm sulfur and nitrogen; less than 2 wt% unsaturates, and 0.001 to 0.3 wt% oxygen, water free basis.

The process of claim 10 further characterized in that the product contains less than 15 ppm dioxygenates.

11. The process of claim 10 further characterized in that the product is blended with petroleum derived feed of similar boiling range. DATED this 29 th day of November, 2000. EXXON RESEARCH AND ENGINEERING COMPANY WATERMARK PATENT TRADEMARK ATTORNEYS 4 T H FLOOR "DURACK CENTRE" oo 263 ADELAIDE TERRACE PERTH WA 6000 *oo *oo o• o*o•