Synthetic jet fuel and process for its production

Information

  • Patent Grant
  • 6309432
  • Patent Number
    6,309,432
  • Date Filed
    Tuesday, June 16, 1998
    26 years ago
  • Date Issued
    Tuesday, October 30, 2001
    23 years ago
Abstract
Clean distillate useful as a jet fuel or jet blending stock is produced from Fischer-Tropsch wax by separating wax into heavier and lighter fractions; further separating the lighter fraction and hydroisomerizing the heavier fraction and that portion of the light fraction above about 475° F. The isomerized product is blended with the untreated portion of the lighter fraction to produce high quality, clean, jet fuel.
Description




FIELD OF THE INVENTION




This invention relates to a distillate material having excellent suitability as a jet fuel with high lubricity or as a blending stock therefor, as well as the process for preparing the jet fuel. More particularly, this invention relates to a process for preparing jet fuel from a Fischer-Tropsch wax.




BACKGROUND OF THE INVENTION




Clean distillates streams that contain no or nil sulfur, nitrogen, or aromatics, are, or will likely be in great demand as jet fuel or in blending jet fuel. Clean distillates having relatively high lubricity and stability are particularly valuable. Typical petroleum derived distillates are not clean, in that they typically contain significant amounts of sulfur, nitrogen, and aromatics. In addition, the severe hydrotreating needed to produce fuels of sufficient stability often results in a fuel with poor lubricity characteristics. These petroleum derived clean distillates produced through severe hydrotreating involve significantly greater expense than unhydrotreated fuels. Fuel lubricity, required for the efficient operation of the fuel delivery system, can be improved by the use of approved 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 complete elimination of oxygenates from the jet fuel.




By virtue of this present invention small amounts of oxygenates are retained, the resulting product having high lubricity. This product is useful as a jet fuel as such, or as a blending stock for preparing jet fuels from other lower grade material.




SUMMARY OF THE INVENTION




In accordance with this invention, a clean distillate useful as a jet fuel or as a jet fuel blend stock and having lubricity, as measured by the Ball on Cylinder (BOCLE) test, approximately equivalent to, or better than, the high lubricity reference fuel is produced, preferably from a Fischer-Tropsch wax and preferably derived from cobalt or ruthenium catalysts, by separating the waxy product into a heavier fraction and a lighter fraction; the nominal separation being, for example, at about 700° F. Thus, the heavier fraction contains primarily 700° F.+, and the lighter fraction contains primarily 700° F.−




The distillate is produced by further separating the lighter fraction into at least two other fractions: (i) one of which contains primary C


7-12


alcohols and (ii) one of which does not contain such alcohols. The fraction (ii) is a 550° F.+ fraction, preferably a 500° F.+ fraction, more preferably a 475° F.+ fraction, and still more preferably a n-C


14


+ fraction. At least a portion, preferably the whole of this heavier fraction (ii), is subjected to hydroconversion (e.g., hydroisomerization) in the presence of a bi-functional catalyst at typical hydroisomerization conditions. The hydroisomerization of this fraction may occur separately or in the same reaction zone as the hydroisomerization of the Fischer-Tropsch wax (i.e., the heavier 700° F.+ fraction obtained from the Fischer-Tropsch reaction) preferably in the same zone. In any event, a portion of the, for example, 475° F.+ material is converted to a lower boiling fraction, e.g., 475° F.− material. Subsequently, at least a portion and preferably all of the material compatible with jet freeze from hydroisomerization is combined with at least a portion and preferably all of the fraction (i) which is preferably a 250-475° F. fraction, and is further preferably characterized by the absence of any hydroprocessing, e.g., hydroisomerization. The jet fuel or jet fuel blending component of this invention boils in the range of jet fuels and may contain hydrocarbon materials boiling above the jet fuel range to the extent that these additional materials are compatible with the jet freeze specification, i.e., −47° C. or lower. The amount of these so-called compatible materials depends on the degree of conversion in the hydroisomerization zone, with more hydroisomerization leading to more of the compatible materials, i.e., more highly branched materials. Thus, the jet fuel range is nominally 250-550° F.; preferably 250-500° F., more preferably 250-475° F. and may include the compatible materials, and having the properties described below.




The jet material recovered from the fractionator has the properties shown in the following table:


















paraffins




at least 95 wt %, preferably at least 96 wt %,







more preferably at least 97 wt %, still more







preferably at least 98 wt %






iso/normal ratio




about 0.3 to 3.0, preferably 0.7-2.0






sulfur




≦50 ppm (wt), preferably nil






nitrogen




≦50 ppm (wt), preferably ≦20 ppm, more







preferably nil






unsaturates




≦2.0 wt %, preferably ≦1.0 wt %, most






(olefins and aromatics)




preferably ≦0.5 wt %






oxygenates




about 0.005 to less than about 0.5 wt % oxygen,







water free basis














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




The oxygenates are contained essentially, e.g.,≧95% of oxygenates, in the lighter fraction, e.g., the 250-475° F. fraction, and are primarily, e.g.,≧95%, terminal, linear alcohols of C


6


to C


12


.











DESCRIPTION OF THE DRAWINGS





FIG. 1

is a schematic of a process in accordance with this invention.











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


, 700° F.+ and 700° F.− respectively. The lighter fraction goes through a hot separator


6


and a 475-700° F. fraction is recovered in line


8


, while a 475° F.-fraction is recovered in line


7


. The 475-700° F. fraction is then recombined with the 700+° F. material from line


3


and fed into the hydroisomerization reactor where a percentage, typically about 50%, is converted to 700° F.− material. The 475° F.− material goes through cold separator


9


from which C


4


− gases are recovered in line


10


. A C


5


-475° F. fraction is recovered in line


11


and is combined with the output from the hydroisomerization reactor,


5


, in line


12


.




Line


12


is sent to a distillation tower where a C


4


-250 ° F. naphtha stream line


16


, a 250-475° F. jet fuel line


15


, a 475-700° F. diesel fuel line


18


, and a 700° F.+ material is produced. The 700° F.+ material may be recycled back to the hydroisomerization reactor


5


or used as to prepare high quality lube base oils. Preferably, the split between lines


15


and


18


is adjusted upwards from 475° F. if the hydroisomerization reactor,


5


, converts essentially all of the n-C


14


+ paraffins to isoparaffins. This cut point is preferably 500° F., most preferably 550° F., as long as jet freeze point is preserved at least at −47° C.




The hydroisomerization process is well known and the table below lists some broad and preferred conditions for this step.




















Condition




Broad Range




Preferred Range













temperature, ° F.




300-800 




500-750







total pressure, psig




300-2500




 500-1500







hydrogen treat rate, SCF/B




500-5000




1500-4000















While virtually any bi-functional catalysts consisting of metal hydrogenation component and an acidic component useful in hydroprocessing (e.g., 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 non-noble metals (e.g., nickel, cobalt) in amounts of 0.5-20 wt %, which may or may not also include a Group VI metals (e.g., molybdenum) in amounts of 1.0-20 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 III, IV, VA or VI oxides, as well as Y sieves, such as ultrastable Y sieves. Preferred supports include alumina and silica-alumina.




A preferred catalyst has a surface area in the range of about 200-500 m


2


/gm, preferably 0.35 to 0.80 ml/gm, as determined by water adsorption, and a bulk density of about 0.5-1.0 g/ml.




This catalyst comprises 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 50 wt %, preferably 5-30 wt %, more preferably 10-20 wt %. Also, the support may contain small amounts, e.g., 20-30 wt %, of a binder, e.g., alumina, silica, Group IVA metal oxides, and various types of clays, magnesia, etc., preferably alumina.




The preparation of amorphous silica-alumina microspheres has been 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.




The catalyst is prepared by co-impregnating the metals from solutions onto the support, drying at 100-150° C., and calcining in air at 200-550° C.




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 VIII metal. A typical catalyst is shown below:





















Ni, wt %




2.5-3.5







Cu, wt %




0.25-0.35







Al


2


O


3


—SiO


2






65-75







Al


2


O


3


(binder)




25-30







Surface Area




290-325 m


2


/gm







Pore Volume (Hg)




0.35-0.45 mL/gm







Bulk Density




0.58-0.68 g/mL















The 700° F.+ conversion to 700° F.− ranges from about 20-80%, preferably 20-70%, more preferably about 30-60%. During hydroisomerization, essentially all olefins and oxygen containing materials are hydrogenated. In addition, most linear paraffins are isomerized or cracked, resulting in a large improvement in cold temperature properties such as jet freeze point.




The separation of the 700° F.− stream into a C


5


-475° F. stream and a 475-700° F. stream and the hydroisomerization of 475-700° F. stream leads, as mentioned, to improved freeze point in the product. Additionally, however, the oxygen containing compounds in the C


5


-475° F. have the effect of improving the lubricity of the resulting jet fuel, and can improve the lubricity of conventionally produced jet fuels when used as a blending stock.




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 products of the Fischer-Tropsch process are primarily paraffinic hydrocarbons. Ruthenium produces paraffins primarily boiling in the distillate range, i.e., C


10


-C


20


; while cobalt catalysts generally produce more of heavier hydrocarbons, e.g., C


20


+, and cobalt is a preferred Fischer-Tropsch catalytic metal.




Good jet fuels generally have the properties of high smoke point, low freeze point, high lubricity, oxidative stability, and physical properties compatible with jet fuel specifications.




The product of this invention can be used as a jet 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 jet product. Although, the product of this invention will improve almost any jet product, it is especially desirable to blend this product with refinery jet streams of low quality, particularly those with high aromatic contents.




By virtue of using the Fischer-Tropsch process, the recovered distillate has essentially nil sulfur and nitrogen. These hetero-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.




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.




We have found, however, that small amounts of oxygenates, preferably alcohols, provide exceptional lubricity for jet fuels. For example, as illustrations will show, a highly paraffinic jet 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 not present, for example, by extraction, absorption 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.




By virtue of the processing scheme disclosed in this invention a part of the lighter, 700° F.− fraction, i.e., the 250° F.-475° F. fraction is not subjected to any hydrotreating. In the absence of hydrotreating of this fraction, the small amount of oxygenates, primarily linear alcohols, in this fraction are preserved, while oxygenates in the heavier fraction are eliminated during the hydro-isomerization step. The valuable oxygen containing compounds, for lubricity purposes, are C


7


+, preferably C


7


-C


12


, and more preferably C


9


-C


12


primary alcohols are in the untreated 250-475° F. fraction. Hydroisomerization also serves to increase the amount of iso-paraffins in the distillate fuel and helps the fuel to meet freeze point specifications.




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 (these 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.




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.




Non-shifting Fischer-Tropsch reactions are well known to those skilled in the art and may be characterized by conditions that minimize the formation of CO


2


by products. 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 180-220° 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, i.e., at least about 0.01 wt % oxygen (water free basis), preferably 0.01-0.5 wt % oxygen (water free basis), more preferably 0.02-0.3 wt % oxygen (water free basis).




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




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 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 C


5


-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 at 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 % Hydrotreated F-T Hot Separator Liquids were combined and rigorously mixed. Jet Fuel A was the 250-475° 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. No. 5,292,989 and U.S. Pat. No. 5,378,348. Hydroisomerization conditions were 708° F., 750 psig H


2


, 2500 SCF/B H


2


, and a liquid hourly space velocity (LHSV) of 0.7-0.8. 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 H


2


, 1000 SCFIB H


2


, and 3.0 LHSV. Fuel A is representative of a typical of a completely hydrotreated cobalt derived Fischer-Tropsch jet 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. Jet Fuel B was the 250-475° 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. No. 5,292,989 and U.S. Pat. No. 5,378,348. Hydroisomerization conditions were 690° F., 725 psig H


2


, 2500 SCF/B 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




To measure the lubricity of this invention against commercial jet fuel in use today, and its effect in blends with commercial jet fuel the following fuels were tested. Fuel C is a commercially obtained U. S. Jet fuel meeting commercial jet fuel specifications which has been treated by passing it over adapulgous clay to remove impurities. Fuel D is a mixture of 40% Fuel A (Hydrotreated F-T Jet) and 60% of Fuel C (U.S. Commercial Jet). Fuel E is a mixture of 40% Fuel B (this invention) and 60% of Fuel C (U.S. Commercial Jet).




EXAMPLE 4




Fuel A from Example 1 was additized with model compound alcohols found in Fuel B of this invention as follows: Fuel F is Fuel A with 0.5% by weight of 1-Heptanol. Fuel G is Fuel A with 0.5% by weight of 1-Dodecanol. Fuel H is Fuel A with 0.05% by weight of 1-Hexadecanol. Fuel I is Fuel A with 0.2% by weight of 1-Hexadecanol. Fuel J is Fuel A with 0.5% by weight of 1-Hexadecanol.




EXAMPLE 5




Jet Fuels A-E were all tested using a standard Scuffing Load Ball on Cylinder Lubricity Evaluation (BOCLE or SLBOCLE), further 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, and in absolute grams of load to scuffing.












TABLE 1











Scuffing BOCLE results for Fuels A-E. Results reported






as absolute scuffing loads and percents of Reference Fuel 2






as described in the above reference.














Scuffing




% Reference






Jet Fuel




Load




Fuel 2









A




1300




19%






B




2100




34%






C




1600




23%






D




1400




21%






E




2100




33%














The completely hydrotreated Jet Fuel A, exhibits very low lubricity typical of an all paraffin jet fuel. Jet Fuel B, which contains a high level of oxygenates as linear, C


5


-C


14


primary alcohols, exhibits significantly superior lubricity properties. Jet fuel C, which is a commercially obtained U. S. Jet Fuel exhibits slightly better lubricity than Fuel A, but is not equivalent to fuel B of this invention. Fuels D and E show the effects of blending Fuel B of this invention. For Fuel D, the low lubricity Fuel A combined with Fuel C, produces a Fuel with lubricity between the two components as expected, and significantly poorer than the F-T fuel of this invention. By adding Fuel B to Fuel C as in Fuel E, lubricity of the poorer commercial fuel is improved to the same level as Fuel B, even though Fuel B is only 40% of the final mixture. This demonstrates the substantial improvement which can be obtained through blending the fuel of this invention with conventional jet fuels and jet fuel components.




EXAMPLE 7




An additional demonstration of the effect of the alcohols on lubricity is shown by adding specific alcohols back to Fuel A with low lubricity. The alcohols added are typical of the products of the Fischer-Tropsch processes described in this invention and found in Fuel B.












TABLE 2











Scuffing BOCLE results for Fuels A and F-J. Results reported






as absolute scuffing loads and percents of Reference Fuel 2






as described the above reference.














Scuffing




% Reference






Jet Fuel




Load




Fuel 2









A




1300




19%






F




2000




33%






G




2000




33%






H




2000




32%






I




2300




37%






J




2700




44%














EXAMPLE 8




Fuels from Examples 1-5 were tested in the ASTM D5001 BOCLE test procedure for aviation fuels. This test measures the wear scar on the ball in millimeters as opposed to the scuffing load as shown in Examples 6 and 7. Results for this test are show for Fuels A, B, C, E, H, and J which demonstrate that the results from the scuffing load test are similarly found in the ASTM D5001 BOCLE test.












TABLE 3











ASTM D5001 BOCLE results for Fuels A, B, C, E, H, J.






Results reported as wear scar diameters as described in ASTM D5001














Jet Fuel




Wear Scar Diameter











A




0.57 mm







B




0.54 mm







C




0.66 mm







E




0.53 mm







H




0.57 mm







J




0.54 mm















Results above show that the fuel of this invention, Fuel B, shows superior performance to either the commercial jet fuel, Fuel C, or the hydrotreated Fischer-Tropsch fuel, Fuel A. Blending the poor lubricity commercial Fuel C with Fuel B results in performance equivalent to Fuel B as was found in the Scuffing Load BOCLE test. Adding very small amounts of alcohols to Fuel A does not improve lubricity in this test as it did in the scuffing load test (Fuel H), but at higher concentration improvement is seen (Fuel J).



Claims
  • 1. A material useful as a jet fuel or as a blending component for a jet fuel comprising: a 250-550° F. fraction derived from a non-shifting Fischer-Tropsch process, said material includingat least 95 wt % paraffins with an iso to normal ratio of about 0.3 to 3.0, ≦50 ppm (wt) each of sulfur and nitrogen less than about 1.0 wt % unsaturates, and about 0.005 to less than 0.5 wt % oxygen, water free basis.
  • 2. The material of claim 1 wherein the oxygen is present primarily as linear alcohols.
  • 3. The material of claim 1 wherein the material is comprised of a 250-500° F. fraction.
  • 4. The material of claim 2 wherein the linear alcohols are C7-C12.
  • 5. The material of claim 2 wherein said linear alcohols are from a source other than said fraction.
  • 6. A jet fuel containing at least 10 wt % of the material of claim 1 as a blending agent.
  • 7. The jet fuel of claim 6 containing at least 40 wt % of the material of claim 1 as a blending agent.
  • 8. The material of claim 1 wherein said oxygen is present in the form of compounds having a hydrogen bonding energy greater than the bonding energy of hydrocarbons.
  • 9. The material of claim 1 wherein said oxygen is present in the form of compounds having a lipophilic end and a hydrophilic end.
  • 10. A material useful as a jet fuel or as a blending component for a jet fuel comprising: a 250-550° F. fraction derived from a non-shifting Fischer-Tropsch process, said material includingat least 95 wt % paraffins with an iso to normal ratio of about 0.3 to 3.0, ≦50 ppm (wt) each of sulfur and nitrogen less than about 1.0 wt % unsaturates, and sufficient oxygen containing compounds so that the material has a lubricity of at least 34% of that of Reference Fuel 2, described in “The U.S. Army Scuffing Load Wear Test”, Lacey, P. I., Jan. 1, 1994 (“Lacey”) when measured by the Scuffing Load Ball on Cylinder Lubricity Evaluation described in Lacey.
  • 11. A process for increasing the lubricity of a jet fuel containing a 250-550° F. fraction derived from a non-shifting Fischer-Tropsch process, comprising:adding 0.005 to 0.5 wt % oxygen, water free basis, of said fraction to said fuel in the form of oxygen containing compounds having a lipophilic end and a hydrophilic end.
  • 12. The process of claim 11 wherein said oxygen containing compounds include linear alcohols.
  • 13. The material of claim 1 wherein the oxygen, on a water free basis, is about 0.02-0.3 wt %.
  • 14. The material of claim 1 wherein the fraction contains di-oxygenates of less than 15 wppm oxygen as oxygen.
  • 15. The material of claim 10 wherein the jet fuel or blending component therefor is a 250-475° F. fraction.
  • 16. The material of claim 15 wherein the fraction contains di-oxygenates of less than 15 wppm oxygen as oxygen.
  • 17. The material of claim 10 wherein the amount of oxygen, water free basis, in the fraction is about 0.02-0.3 wt %.
  • 18. The process of claim 11 wherein the amount of oxygen containing compounds, water free basis, is about 0.02-0.3 wt %.
  • 19. The process of claim 11 wherein the fraction contains di-oxygenates of less than 15 wppm oxygen as oxygen.
CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of Ser. No. 798,378, filed Feb. 7, 1997, now U.S. Pat. No. 5,766,274.

US Referenced Citations (182)
Number Name Date Kind
2243760 Martin May 1941
2562980 Atwell Aug 1951
2668790 Good et al. Feb 1954
2668866 Good et al. Feb 1954
2756183 Knox, Jr. Jul 1956
2779713 Cole et al. Jan 1957
2817693 Koome et al. Dec 1957
2838444 Teter et al. Jun 1958
2888501 Folkins et al. May 1959
2892003 Weisz Jun 1959
2906688 Farmer et al. Sep 1959
2914464 Burton et al. Nov 1959
2982802 Folkins et al. May 1961
2993938 Bloch et al. Jul 1961
3002827 Fenske Oct 1961
3052622 Johnson et al. Sep 1962
3078323 Kline et al. Feb 1963
3121696 Hoekstra Feb 1964
3123573 Carr Mar 1964
3125511 Tupman et al. Mar 1964
3147210 Hass et al. Sep 1964
3206525 Michaels et al. Sep 1965
3253055 Goble et al. May 1966
3268436 Arey, Jr., et al. Aug 1966
3268439 Tupman et al. Aug 1966
3308052 Ireland et al. Mar 1967
3338843 Goble et al. Aug 1967
3340180 Beuther et al. Sep 1967
3365390 Egan et al. Jan 1968
3395981 Kischio Aug 1968
3404086 Plank et al. Oct 1968
3471399 O'Hara Oct 1969
3486993 Egan et al. Dec 1969
3487005 Egan et al. Dec 1969
3507776 Hann Apr 1970
3530061 Orkin et al. Sep 1970
3594307 Kirk, Jr. Jul 1971
3607729 Robinson et al. Sep 1971
3619408 Larson Nov 1971
3620960 Kozlowski et al. Nov 1971
3629096 Divijak, Jr. Dec 1971
3630885 Egan Dec 1971
3658689 Steinmetz et al. Apr 1972
3660058 Feldman et al. May 1972
3668112 Parker Jun 1972
3668113 Burbidge Jun 1972
3674681 Lyon Jul 1972
3681232 Egan Aug 1972
3684695 Neel et al. Aug 1972
3692695 Suggitt et al. Sep 1972
3692697 Kravitz et al. Sep 1972
3709817 Suggitt et al. Jan 1973
3711399 Estes et al. Jan 1973
3717586 Suggitt et al. Feb 1973
3725302 Shimely Apr 1973
3761388 Bryson et al. Sep 1973
3767562 Sze et al. Oct 1973
3770618 Adams Nov 1973
3775291 Sze Nov 1973
3794580 Ladeur Feb 1974
3814682 Christman et al. Jun 1974
3830723 Ladeur et al. Aug 1974
3830728 Mounce Aug 1974
3840508 Ballard et al. Oct 1974
3840614 Kravitz et al. Oct 1974
3843509 Suto et al. Oct 1974
3843746 Kravitz et al. Oct 1974
3848018 Robson Nov 1974
3852186 Christman et al. Dec 1974
3852207 Stangeland et al. Dec 1974
3861005 Steinmetz et al. Jan 1975
3864425 Gardner Feb 1975
3870622 Ashton et al. Mar 1975
3876522 Campbell et al. Apr 1975
3887455 Hamner Jun 1975
3915843 Franck et al. Oct 1975
3963601 Hilfman Jun 1976
3976560 Erickson Aug 1976
3977961 Hamner Aug 1976
3977962 Arey, Jr. et al. Aug 1976
3979279 Yan Sep 1976
4014821 Hamner Mar 1977
4032304 Dorer Jr., et al. Jun 1977
4032474 Goudriaan et al. Jun 1977
4041095 Kuo Aug 1977
4051021 Hamner Sep 1977
4059648 Derr et al. Nov 1977
4067797 Chen Jan 1978
4073718 Hamner Feb 1978
4087349 Baird, Jr. May 1978
4125566 Dinh Nov 1978
4139494 Itoh et al. Feb 1979
4162962 Stangeland Jul 1979
4186078 Itoh et al. Jan 1980
4212771 Hamner Jul 1980
4263127 Rausch et al. Apr 1981
4304871 Brennan et al. Dec 1981
4342641 Reif et al. Aug 1982
4378973 Sweeney Apr 1983
4390414 Cody Jun 1983
4394251 Miller Jul 1983
4427534 Brunn et al. Jan 1984
4427791 Miale Jan 1984
4428819 Shu et al. Jan 1984
4444895 Fung et al. Apr 1984
4451572 Cody May 1984
4472529 Johnson et al. Sep 1984
4477586 McDaniel Oct 1984
4518395 Petronella May 1985
4527995 Itow et al. Jul 1985
4529526 Inoue et al. Jul 1985
4539014 Sweeney Sep 1985
4568663 Mauldin Feb 1986
4579986 Sie Apr 1986
4588701 Chiang May 1986
4594172 Sie Jun 1986
4599162 Yen Jul 1986
4608151 Miller Aug 1986
4618412 Hudson et al. Oct 1986
4627908 Miller Dec 1986
4645585 White Feb 1987
4673487 Miller Jun 1987
4684756 Derr, Jr. et al. Aug 1987
4695365 Ackelson Sep 1987
4755280 Hudson et al. Jul 1988
4764266 Chen et al. Aug 1988
4804802 Evans Feb 1989
4832819 Hamner May 1989
4851109 Chen et al. Jul 1989
4855530 LaPierre et al. Aug 1989
4875992 Hamner Oct 1989
4900707 Cody et al. Feb 1990
4906599 Cody et al. Mar 1990
4911821 Katzer et al. Mar 1990
4919786 Hamner Apr 1990
4919788 Chen et al. Apr 1990
4923841 Hamner May 1990
4929795 Cody et al. May 1990
4937399 Wachter et al. Jun 1990
4943672 Hamner Jul 1990
4959337 Cody et al. Sep 1990
4960504 Pellet et al. Oct 1990
4962269 LaPierre et al. Oct 1990
4982031 Chen Jan 1991
4990713 Le et al. Feb 1991
4992159 Cody Feb 1991
4992406 Mauldin et al. Feb 1991
5037528 Garwood et al. Aug 1991
5059299 Cody Oct 1991
5059741 Foley Oct 1991
5110445 Chen et al. May 1992
5156114 Gunnerman Oct 1992
5157187 Le et al. Oct 1992
5158671 Cody et al. Oct 1992
5183556 Reilly et al. Feb 1993
5187138 Davis Feb 1993
5281347 Igarashi et al. Jan 1994
5282958 Santilli et al. Feb 1994
5292988 Wu Mar 1994
5292989 Davis Mar 1994
5302279 Degnan et al. Apr 1994
5306860 Bigeard et al. Apr 1994
5308365 Kesling May 1994
5324335 Benham Jun 1994
5345019 Bigeard et al. Sep 1994
5348982 Herbolzheimer et al. Sep 1994
5362378 Borghard et al. Nov 1994
5370788 Dai Dec 1994
5378249 Morrison Jan 1995
5378348 Davis et al. Jan 1995
5378351 Guichard et al. Jan 1995
5385588 Brennan Jan 1995
5479775 Kraemer et al. Jan 1996
5500449 Benham et al. Mar 1996
5504118 Benham et al. Apr 1996
5506272 Benham et al. Apr 1996
5522983 Cash et al. Jun 1996
5538522 Ahmed Jul 1996
5543437 Benham et al. Aug 1996
5545674 Behrmann et al. Aug 1996
5689031 Berlowitz et al. Nov 1997
5766274 Willenbrink et al. Jun 1998
Foreign Referenced Citations (77)
Number Date Country
275062 Sep 1964 AU
539698 Apr 1957 CA
700237 Dec 1964 CA
954058 Mar 1974 CA
3030998 Jan 1982 DE
P3030998.9 Jan 1982 DE
2251156 Apr 1993 DE
0113045A1 Jul 1984 EP
0153782 Apr 1985 EP
0227218A1 Jan 1987 EP
0266898A2 May 1988 EP
0281992A3 Sep 1988 EP
0323092 Dec 1988 EP
0321301A3 Jun 1989 EP
0321303 Jun 1989 EP
0418860A1 Mar 1991 EP
0374461B1 May 1992 EP
0532118 Mar 1993 EP
0515270A1 Mar 1993 EP
0532117A1 Mar 1993 EP
0532117 Mar 1993 EP
0515256A1 Mar 1993 EP
0542528A1 May 1993 EP
0441014B1 Jul 1993 EP
0555006A1 Aug 1993 EP
0566348A Oct 1993 EP
0566348A2 Oct 1993 EP
0587245A1 Mar 1994 EP
0587246 Mar 1994 EP
0634472A1 Jan 1995 EP
0460957B1 Feb 1995 EP
0668342A1 Aug 1995 EP
0753563A1 Jan 1997 EP
0569228B1 Jun 1998 EP
732964 Nov 1932 FR
859686 Aug 1939 FR
2137490 Apr 1972 FR
2650289 Jan 1991 FR
728543 Apr 1955 GB
823010 Apr 1959 GB
848198 Sep 1960 GB
953188 Mar 1964 GB
953189 Mar 1964 GB
951997 Nov 1964 GB
1065205 Apr 1967 GB
1306646 Feb 1973 GB
1342499 Mar 1974 GB
1342500 Mar 1974 GB
1381004 Jan 1975 GB
1440230 Jun 1976 GB
1460476 Jun 1977 GB
1493928 Nov 1977 GB
1499570 Jan 1978 GB
49035323 Feb 1952 JP
2302561 Dec 1990 JP
6200262 Jul 1991 JP
H3-231990 Oct 1991 JP
2-302561 Oct 1991 JP
7310096 May 1994 JP
9202601 Feb 1992 WO
9214804 Mar 1992 WO
9201769 Jun 1992 WO
9417160 Aug 1994 WO
9428095 Aug 1994 WO
9420593 Sep 1994 WO
9502695 Jan 1995 WO
9503377 Feb 1995 WO
9506695 Mar 1995 WO
9527021 Oct 1995 WO
9703750 Feb 1996 WO
9623855 Aug 1996 WO
9626996 Sep 1996 WO
9704044 Feb 1997 WO
WO9714769 Apr 1997 WO
9714768 Apr 1997 WO
9714769 Apr 1997 WO
9721787 Jun 1997 WO
Non-Patent Literature Citations (44)
Entry
Ward, “Compos. of F-T Diesel Fuel”, Div. Pet. Chem. 117th Mtg. ACS (1950).
Morgan et al., “Some Comparative Chemical, Physical and Compatibility Properties of Sasol Slurry Phase Distillate Fuel”, SAE No. 982488 (1998), pp. 1-9.
Agee, “A New Horizon For Synthetic Fuels”, World Conference on Transportation Fuel Quality Oct. 6-8, 1996.
Norton et al., “Emissions from Trucks using Fischer-Tropsch Diesel Fuel”, SAE No. 982526, pp. 1-10 (1998).
Booth et al., (Shell) “Severe hydrotreating of diesel can cause fuel-injector pump failure”, PennWell Publishing Company, Oil & Gas Journal (Aug. 16, 1993).
The Clean Fuels Report, “Volvo Demonstrates Benefits of Reformulated Diesel” “Research and Technology”, pp. 166-170, Sep. 1995.
The Clean Fuels Report, “Cetane Number is Major Control for Diesel Emissions with Catalyst”, pp. 170-173, Sep. 1995.
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 Meeting, Michigan, May 6-8, 1996.
Erwin et al., “The Standing of Fischer-Tropsch Diesel in an Assay of Fuel Performance and Emissions”, Southwest Research Institute, Contract Number NREL SUB YZ-2-113215-1 (Oct. 26, 1993).
M'Hamdi et al., “Packed Column SFC of Gas Oils”, J. High Resol. Chromatogr., vol. 21, pp. 94-102 (Feb. 1998).
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).
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).
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.
Lee et al., “Development of a Supercritical Fluid Chromatographic Method for Determination of Aromatics in Heating Oils and Diesel Fuels,”, Energy & Fuels, 3, pp. 80-84 (1989), American Chemical Society.
T.L. Ullman, “Effects of Cetane Number, Cetane Improver, Aromatics, and Oxygenates on 1994 Heavy-Duty Diesel Engine Emissions”, SAE Paper 941020.
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.
T. L. Ullman, “Effects of Cetane Number on Emissions From a Prototype 1998 Heavy-Duty Diesel Engine”, SAE Paper 950251.
J. S. Freely, “Abatement of NOx from Diesel Engines: Status & Technical Challenges”, SAE Paper 950747.
J. Leyer, “Design Aspects of Lean NOx Catalysts for Gasoline & Diesel Applications”, SAE Paper 952495.
M. Kawanami, “Advanced Catalyst Studies of Diesel NOx Reduction for On-Highway Trucks”, SAE Paper 950154.
Anderson, “Det. of Ox and Olefin Compd Types by IR...”, Analyt. Chem., vol. 20, No. 11 (Nov. 1946), pp. 998-1006.
Bruner, “Syn. Gasoline From Nat. Gas”, Ind. & Eng. Chem. vol. 41, No. 11 (1948), pp. 2511-2515.
Bryant, “Impr. Hydroxylamine Meth. for Det. Aldeh. & Ketones...”, p. 57 (Jan. 1935).
DuBois, “Det. of Bromine Addition Numbers”, Analyt. Chem., vol. 20, No. 7, pp. 624-627 (1948).
Friedel, “Compos. of Synth. Liquid Fuels. I...”, JACS 72, pp. 1212-1215 (1950).
Johnston, “Det. of Olefins in Gasoline”, Analyt. Chem. 805-812 (1947).
Niederl, “Micromethods of Quantitative Organic Analysis”, pp. 263-272, 2nd et. (J. Wiley & Sons, NY 1942).
Puckett, “Ignition Qualities of HC in the Diesel Fuel Boiling Range” in Information Circular Bureau of Mines 7474 (Jul. 1948).
Smith, “Rapid Det. of Hydroxyl...”, p. 61 (Jan. 1935).
Tilton, “Prod. of High Cetane Number Diesel Fuels by Hydrogenation”, Ind. & Eng. Chemistry, vol. 40, pp. 1270-1279 (Jul. 1948).
Underwood, “Industrial Synthesis of HC from Hydrogen and Carbon Monixide”, Ind. & Eng. Chemistry, vol. 32, No. 4, pp. 450-454.
Ward, “Superfractionation Studies”, Ind. & Eng. Chem. vol. 39, pp. 105-109 (109th ACS meeting).
Wheeler, “Peroxide Formation as a Meas. of Autoxidative Determination”, Oil & Soap 7, 87 (1936).
Eiler, “Shell Middle Dist.”, Cat. Letters 7, 253-270 (1990).
Lanh, J. Cat., 129, 58-66 (1991), Convers. of Cyclohexane... .
Rappold, “Industry pushes use of PDC bits...”, J. Oil & Gas, Aug. 14, 1995.
Shah et al., USDOE/USDOC NTIS, UOP, Inc., Fischer-Tropsch Wax Characterization and Upgrading -Final Report, DE 88-014638, Jun., 1988 (“UOP Report”).
Signer, The Clean Fuels Report, “Southwest Research Institute Study Delineates The Effect of Diesel Fuel Composition on Emissions”, pp. 153-158 (Jun. 1995).
Lacy, “The U.S. Army Scuffing Load Wear Test”, Jan. 1, 1994.
Ryland et al., “Cracking Catalyst”, Catalysis vol. VII, P. Emmett, ed., Reinhold Publ. NY (1960), pp. 5-9.
Stournas, “Eff. of Fatty Acids...”, JAOC S 72 (4) (1995).
Lacey, Paul I., “Wear Mechanism Evaluation and Measurement in Fuel-Lubricated Components”, Sep., 1994.
SwRI Gear Oil Scuff Test (GOST) Flyer, Gear Oil Scuff Test (GOST), Feb., 1997.
Lacey, Paul I., “Wear Mechanism Evaluation and Measurement in Fuel-Lubricated Components”, U.S. Department of Commerce # ADA284870, Sep. 1994.
Continuation in Parts (1)
Number Date Country
Parent 08/798378 Feb 1997 US
Child 09/098231 US