[go: up one dir, main page]

WO1995011873A1 - Distillats moyens constituant des carburants a haut rendement - Google Patents

Distillats moyens constituant des carburants a haut rendement Download PDF

Info

Publication number
WO1995011873A1
WO1995011873A1 PCT/US1994/009960 US9409960W WO9511873A1 WO 1995011873 A1 WO1995011873 A1 WO 1995011873A1 US 9409960 W US9409960 W US 9409960W WO 9511873 A1 WO9511873 A1 WO 9511873A1
Authority
WO
WIPO (PCT)
Prior art keywords
diamondoid
composition
less
weight percent
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1994/009960
Other languages
English (en)
Inventor
Catherine S. H. Chen
Harold S. Chung
Andrew Jackson
Ross Allen Kremer
Steven Edward Wentzek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mobil Oil AS
Original Assignee
Mobil Oil AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil AS filed Critical Mobil Oil AS
Priority to AU78308/94A priority Critical patent/AU7830894A/en
Publication of WO1995011873A1 publication Critical patent/WO1995011873A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • This invention relates to the field of petroleum-based middle distillate fuels. More specifically, this invention provides fuel compositions having improved viscosity stability, enhanced heat capacity per unit volume, and lower cloud point.
  • Jet fuels are employed in a method of combustion wherein fuel is continuously introduced into and continuously burned in a confined space, for the purpose of deriving power directly from the hot products of combustion.
  • Jet engines typically consist of a propulsion or jet tube, plus a gas turbine which extracts sufficient energy from the departing gases to drive the compressor.
  • the compressor and turbine are assembled axially upon a common shaft, spaced far enough apart to permit a number of combustion chambers to be arranged about the shaft between the compressor and turbine, with an exhaust tube extending rearwardly from the turbine.
  • the principal application of such engines is in powering aircraft, particularly for high-altitude operations. For these reasons, the desiderata of fuels useful in jet combustion devices are many and varied.
  • Jet combustion fuels are hydrocarbon fractions that can have initial boiling points as low as about 200°F (93°C), or lower, and end-boiling points as high as about 600°F (315°C).
  • a jet fuel can boil within a relatively low range of temperatures or within a relatively high range of temperatures.
  • jet combustion fuels that boil within rather low temperature ranges are used.
  • These fuels however, have a high A.P.I. Gravity (or low density), and accordingly, they will have less weight per gallon.
  • the weight per gallon together with the number of b.t.u. per unit weight is determinative of the amount of energy per gallon of fuel, it is desirable to have the density as high as possible.
  • JP-8X A new jet fuel, JP-8X, has been proposed, which has an energy density much high than that of the current JP-8 fuel.
  • Viscosity Index is the most common measure that is applied to the decrease in viscosity of petroleum oils with increasing temperature.
  • a series of Pennsylvania oils exhibiting relatively small change in viscosity with changing temperature is arbitrarily assigned a VI of 100, whereas a series of Gulf Coast oils whose viscosities change relatively greatly is assigned a VI of 0. From the viscosity measurements at 40° and 100°C, the VI of any oil sample can be obtained from detailed tables published by the ASTM (ASTM D-2270) . 14 Kirk-Othmer Encyclopedia of Chemical Technology 489 (Wiley, 1981) . U.S. Patent 4,913,794 to Le et al.
  • U.S. Patent 5,043,503 to Del Rossi et al. discloses alkylated polycycloparaffinic compounds useful as lubricating stocks which are prepared by alkylating a polycycloparaffinic compound in the presence of a catalyst having a Constraint Index of from about 1 to about 10.
  • U.S. Patent 5,053,568 to Chen teaches a lubricant additive and composition comprising the copolymer of 1- vinyladamantane and a l-alkene having from about 4 to about 16 carbon atoms, wherein the copolymer has a Viscosity Index of at least about 80 and a kinematic viscosity of at least about 6 cS at 212°F.
  • the literature discloses traction fluids containing polycyclic compounds which are characterized by a relatively low Viscosity Index.
  • U.S. Patent 5,085,792 to Narihiko et al. relates to a synthetic traction fluid comprising two substituted cyclohexane nuclei connected through an ester linkage.
  • U.S. Patent 5,107,041 to Abe et al. relates to a synthetic traction fluid derived from a 1,1-dicyclohexyl cycloalkane.
  • the hydrogenated dimer of alpha-methyl-styrene (2,4- dicyclohexyl-2-methylpentane) has a VI of only 9.
  • the present invention provides a diamondoid-based composition which is a useful energy density-enhancing additive for a middle distillate fuel such as jet or diesel fuel.
  • the invention further provides a diamondoid- containing middle distillate fuel having enhanced energy density.
  • the additive of the present invention improves the energy density of a middle distillate fuel while maintaining or improving the freeze point and pour points of the resulting mixture. This behavior is surprising and unexpected because it is generally accepted that energy density-enhancing additives generally have low Viscosity Indices, typically within the range of from about -50 to about +50, and high freeze points, and must be diluted with a lighter (lower average molecular weight) solvent to attain the desired low temperature characteristics.
  • the present invention provides a liquid hydrocarbon combustion fuel comprising a distillate fuel or fuel oil together with a diamondoid-based additive composition which has been processed to remove at least a portion of organics having fewer than 10 carbon atoms, said diamondoid-based composition comprising at least about 65 weight percent alkyl-substituted diamondoid compounds which have more than one quaternary carbon atom per molecule and less than about 35 weight percent of diamondoid compounds which have less than two quaternary carbon atoms per molecule.
  • the hydrocarbon combustion fuel of the invention preferably contains less than about 1 weight percent non-hydrocarbons.
  • Examples of diamondoid compounds which contain more than one quaternary carbon include 1,3-dimethyladamantane; 1,3,5-trimethyladamantane; 1,3,5,7-tetramethyladamantane; cis- and trans-1,3,4-trimethyladamantane; 1,2,5,7- tetramethyladamantane; 4,9-dimethyldiamantane; 1,4- dimethyldiamantane; 2,4-dimethyldiamantane; and 4,8- dimethyldiamantane.
  • the diamondoid-based additive of the invention preferably contains more than 80 weight percent of diamondoid compounds having more than one quaternary carbon atom per molecule and less than 20 weight percent of diamondoids having fewer than two quaternary carbon atoms per molecule.
  • the diamondoid-based additive composition of the invention may suitably comprise a major portion of diamondoid compounds, for example, at least about 80 weight percent.
  • the additive composition preferably contains at least about 90 weight percent diamondoid compounds and more preferably contains 98 weight percent or more of diamondoid compounds.
  • the fuel oil or distillate fuel component of the diamondoid-containing middle distillate fuel of the invention are hydrocarbon fractions having an initial boiling point of at least about 250°F (121°C) and an end- boiling point no higher than about 750°F (399°C) and boiling substantially continuously throughout their distillation range.
  • Such fuel oils are generally known as distillate fuel oils. It is to be understood, however, that this term is not restricted to straight run distillate fractions.
  • the distillate fuel oils can be straight run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight run distillate fuel oils, naphthas and the like, with cracked distillate stocks.
  • fuel oils can be treated in accordance with well-known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.
  • distillate fuel oils are characterized by their relatively low viscosities, pour points, and the like.
  • the principal property which characterizes the contemplated hydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range will lie between about 250°F (121°C) and about 750°F (399°C). Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
  • Contemplated among the fuel oils are Nos. 1, 2 and 3 fuel oils used in heating and as diesel fuel oils, and the jet combustion fuels.
  • the domestic fuel oils generally conform to the specification set forth in A.S.T.M.
  • the additive composition of the invention behaves in an unusual and surprising manner at low temperatures. Specifically, the additive composition of the invention can be distilled to remove lower-boiling components without significantly increasing its freeze point but markedly increasing its specific gravity and energy density. This unusual characteristic is of critical importance to its properties as a diamondoid-based additive because previously known high density fuel mixtures required dilution with lower-density hydrocarbons (such as cyclohexane) to maintain an acceptably low freeze point.
  • the additive composition of the invention is generally characterized by a freeze point of less than 0°C, more specifically less than -65°C.
  • the liquid hydrocarbon combustion fuel of the invention is a useful fuel for combustion drivers including, but not limited to, rocket and gas turbine engines, examples of which include ramjet, turbojet and turboprop engines, as well as internal combustion engines, such as diesel engines.
  • Non-hydrocarbons may be removed from the hydrocarbon combustion fuel by any suitable step, for example selective sorption, distillation, or stripping.
  • suitable step for example selective sorption, distillation, or stripping.
  • useful sorbents include activated carbon and activated alumina. Distillation may also be used to remove non-hydrocarbons and is particularly preferred when the distillation conditions are controlled as disclosed herein to remove both hydrocarbons having fewer than 10 carbon atoms as well as non-hydrocarbons.
  • FIG 1 is a Simdis chromatograph of the vacuum distilled diamondoid mixture of Examples I and II.
  • the term "Simdis” as used herein refers to a standard gas chromatography procedure described in ASTM D 2887-84, which is entitled “Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography”.
  • Figure 2 is a Simdis chromatograph of the liquid portion of the centrifuged diamondoid mixture of Example III.
  • Figure 3 is a Simdis chromatograph of the high density fuel mixture of Example IV.
  • Figure 4 is a Simdis chromatograph of the naturally occurring liquid diamondoid mixture of Example V.
  • Figure 5 is a Simdis chromatograph of the hydrotreated diamondoid mixture of Example VI.
  • Figure 6 is a Simdis chromatograph of the diamondoid mixture of Example VII.
  • Figure 7 is a Simdis chromatograph of the diamondoid mixture of Example VIII.
  • Figure 8 is a Simdis chromatograph of the diamondoid mixture of Example IX.
  • Figure 9 is a GC trace of the diamondoid mixture of Example X using a capillary column (Supelco Inc., SPB-1, 0.32 ID, 60 M, 1.0 urn) .
  • Figure 10 is a GC trace of the diamondoid mixture of Example X following the short-path distillation in a Kugelrohr apparatus of Example XI.
  • Figure 11 is a GC trace of the remaining diamondoids produced in Example X after the sample of Example I was purged with a nitrogen stream at room temperature at a rate of 20CC/min.
  • Figures 12A-12C are the GC traces of the adamantane, diamantane, and triamantane/tetramantane fractions, respectively which were separated in accordance with Example XIV.
  • Figure 13 shows energy density and freeze point as functions of specific gravity for the compositions of the present invention in the absence of added hydrocarbon containing fewer than 10 carbon atoms.
  • This invention includes a diamondoid-based additive composition, a liquid hydrocarbon combustion fuel, and a method for operating a combustion-powered driver.
  • the liquid hydrocarbon fuels of the invention exhibit unusual low temperature properties as described above.
  • the additive of the invention is preferably free of non- hydrocarbons including polar sulfur compounds or polar corrosion inhibitors as well as naturally occurring color bodies. These polar compounds may be removed via sorptive media including gamma-alumina, activated charcoal, sand, and clay, merely to name a few.
  • the diamondoid compound- containing additive composition may optionally be hydrotreated to reduce total sulfur and/or to improve color to meet the requirements of the applicable fuel specifications.
  • the diamondoid-based additive composition of the invention may be further processed (e.g., distilled) to remove lower-boiling diamondoid fractions to increase its energy density while maintaining substantially constant freeze point.
  • the diamondoid-based additive composition of the invention may be hydrotreated, but is preferably treated with one or both of two milder conditioning steps.
  • the hydrotreating step is preferably replaced with a simple selective sorption or distillation step.
  • Distillation Process Step The recovered diamondoid compound-containing mixture is charged to a separation stage under vacuum conditions ranging from about 0.05 to about 25 torr (about 66.7 Pa to about 3,330 Pa), preferably from about 0.1 to about 10 torr (about 13.3 Pa to about 1,333.2 Pa), most preferably from about 0.2 to about 2 torr (about 26.7 to about 266.6 Pa).
  • the separation stage is suitably contained in a vessel rated for full vacuum service under the operating temperature selected from the range of about 0°C to about 150"C.
  • the separation stage is preferably connected to a receiver by heated lines of relatively large diameter to avoid condensation or sublimation of valuable products before the products reach the receiver.
  • the distillation vessel may suitably comprise a flash drum rated for full vacuum service at the endpoint temperature of the diamondoid compound-containing mixture.
  • a vessel equipped with suitable heating means, such as external or internal steam or electric heating coils and a temperature controller would be a useful distillation vessel.
  • the distillation vessel more preferably provides more than one theoretical distillation stage and more preferably provides 10 or more stages in a perforated-plate or packed bed-containing column.
  • the column and associated overhead product recovery conduit are preferably equipped with temperature control to prevent sublimation of solids in the column and overhead product recovery conduit.
  • the separation stage is filled with the crude recovered diamondoid compound-containing mixture and the temperature is raised incrementally and/or pressure is decreased until a vapor product flow is detected, at which point the temperature and pressure are held constant until the vapor product flow ceases.
  • the pot temperature is then raised and/or the pressure is decreased to continue separation.
  • the diamondoid-based additive composition of the invention exhibits unusual freeze point behavior upon distillation. Distilling the composition of the invention to remove lower boiling (less dense, lower molecular weight) fractions increases the energy density and the specific gravity of the mixture without significantly increasing the freeze point of the mixture.
  • Previously known energy density-improving additive compositions compromised energy density to meet a freeze point specification by blending a high energy density component with a low freeze point diluent such as cyclohexane.
  • the diamondoid-based additive composition of the present invention requires no such compromise.
  • Figure 13 shows the energy density and freeze point of an embodiment of the invention as a function of specific gravity. The actual freeze points of the mixtures were well below the stated minimum of the measurement method and are therefore shown as downwardly pointing arrows. This behavior stands in marked contrast to that of previously known energy density- improving additives which require the addition of a low freeze point diluent.
  • the sorption step may suitably be conducted at ambient temperature and atmospheric pressure, but may also be conducted under elevated conditions of temperature and pressure.
  • suitable temperatures for the sorption step range from about 20 to about 50°C
  • suitable pressures range from about atmospheric 14.696 psi (101 kPa) to about 100 psia (689 kPa) .
  • the diamondoid-containing additive mixture may optionally be treated under hydrogen pressure in the presence of a hydrotreating catalyst of the type typically used in the petroleum refining industry for desulfurization, denitrogenation, and demetallation of hydrocarbonaceous feedstocks. This step is optional and is not required to meet high density fuel specifications if the sorption and/or distillation steps are conducted as disclosed herein.
  • Suitable catalysts include metals on an inert or catalytically active support as a heterogeneous catalyst.
  • Useful heterogeneous catalysts may contain metals from Groups IVA or VIIIA of the Periodic Table of the Elements, published by Sargent-Welch of Skokie, Illinois (catalog no. S-18806) .
  • Sulfides and oxides of these metals are also useful catalyst components. Specific examples of useful metals, metallic oxides and sulfides within these groups are exemplified by sulfides and oxides of Ni, Mo, W, Co, Pt, Pd, Cu, and Cr.
  • Bimetallic catalysts including Ni-Mo, Ni-W, Co-Mo, and Cu-Cr are particularly preferred.
  • Both inert and catalytically active binders may be employed, with examples including one or more of alumina, silica, silica-alumina, zeolites, clays, Kieselguhr, and active carbons from sources such as coal, coke, and coconut shell.
  • Suitable zeolites include those commonly referred to as large pore, i.e., those zeolites having a Constraint Index of less than about 1, such as zeolite X, and zeolite Y as well as those commonly referred to as medium-pore, i.e., those zeolites having a Constraint Index of from about 1 to about 12.
  • suitable medium-pore zeolites include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.
  • Zeolite Beta known to exhibit characteristics of either a large pore zeolite or a medium- pore zeolite, is also useful in the present invention.
  • the zeolite-containing catalysts useful in the hydrotreating process of the present invention more preferably include those catalysts which exhibit Constraint Indices of from about 0.1 to about 10, for example ZSM-5, MCM-22 and Zeolite Beta, although it is well recognized that the Constraint Index of zeolite Beta varies widely with temperature.
  • Zeolite Beta is described in U.S. Patents 4,696,732; 3,308,069, as well as Re. 28,341, the entire contents of which are incorporated by reference as if set forth at length herein.
  • Constraint Index A convenient measure of the extent to which a zeolite provides control to molecules of varying sizes to its internal structure is the Constraint Index of the zeolite.
  • the method by which the Constraint Index is determined is described in U.S. Patent Number 4,016,218, incorporated herein by reference for details of the method.
  • U.S. Patent Number 4,696,732, cited above, discloses Constraint Index values for typical zeolite materials and is incorporated by reference as if set forth at length herein for detailed catalyst descriptions and Constraint Index values.
  • Zeolite ZSM-5 and the conventional preparation thereof are described in U.S. Patent Number 3,702,886, the disclosure of which is incorporated herein by reference.
  • Other preparations for ZSM-5 are described in U.S. Patent Numbers Re. 29,948 (highly siliceous ZSM-5) ; 4,100,262 and 4,139,600, the disclosure of these is incorporated herein by reference.
  • Zeolite ZSM-12 and the conventional preparation thereof are described in U.S. Patent Number
  • Catalysts such as ZSM-5 combined with a Group VIII metal described in U.S. Patent No. 3,856,872, incorporated by reference as if set forth at length herein, are also useful in the present invention.
  • Additional catalytic materials useful in the present invention include materials which are readily identified by their characteristic X-ray diffraction patterns, such as the PSH-3 composition of U.S. Patent No. 4,439,409, incorporated herein by reference, and MCM-22, the synthesis and composition of which is taught in U.S. Patent 4,954,325, both of which patents are incorporated by reference as if set forth at length herein.
  • the zeolite hydrotreating catalyst herein can also be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed.
  • Such component can be introduced in the catalyst composition by way of cocrystallization, exchanged into the
  • Such component can be impregnated in, or on, the zeolite such as, for example, by, in the case of platinum, treating the zeolite with a solution containing a platinum metal-containing ion.
  • suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
  • the zeolite can be beneficially converted to another form by thermal treatment.
  • This thermal treatment is generally performed by heating one of these forms at a temperature of at least about 370"C for at least 1 minute and generally not longer than 20 hours. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is preferred simply for reasons of convenience.
  • the thermal treatment can be performed at a temperature of up to about 925°C.
  • the zeolite crystals Prior to its use in the hydrotreating process of this invention, the zeolite crystals should be dehydrated, at least partially. This can be done by heating the crystals to a temperature in the range of from about 200"C to about 595°C in an atmosphere such as air, nitrogen, etc.
  • the zeolite crystals can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product such as an extrudate having a particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion, the crystals can be extruded before drying or partially dried and then extruded.
  • the crystalline material may be desired to incorporate with another material which is resistant to the temperatures and other conditions employed in the hydrotreating process of this invention.
  • Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Use of a material in conjunction with the zeolite, i.e., combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the catalyst.
  • Inactive materials suitably serve as diluents to control the amount of conversion so that hydrotreated products can be obtained economically and orderly without employing other means for controlling the rate of reaction.
  • These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin. Said materials, i.e., clays, oxides, etc., function as binders for the catalyst. These clay binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
  • Naturally occurring clays which can be composited with zeolite crystals include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with the zeolite also include inorganic oxides, notably alumina.
  • the crystals can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica- thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina- zirconia silica-alumina-magnesia and silica-magnesia- zirconia. It may also be advantageous to provide at least a part of the foregoing matrix materials in colloidal form so as to facilitate extrusion of the bound catalyst component(s) .
  • a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica- thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-
  • the relative proportions of finely divided crystalline material and inorganic oxide matrix vary widely, with the crystal content ranging from about 1 to about 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight percent of the composite.
  • the stability of the hydrotreating catalyst of the invention may be increased by steaming.
  • U.S. Patent Nos. 4,663,492; 4,594,146; 4,522,929; and 4,429,176 the entire disclosures of which are incorporated herein by reference, describe conditions for the steam stabilization of zeolite catalysts which can be utilized to steam-stabilize the catalyst.
  • the optional hydrotreating step may suitably be conducted under the conditions listed below in Table 1. TABLE 1
  • WHSV based on catalyst. 0.01-100 0.1-5 Pressure, kPa 100-14,000 170-7000 Hydrogen Dosage, Mols H 2 /Mol diamondoid mixture 0.05-100 1-10
  • Example I A mixture of diamondoid compounds recovered from a diamondoid-containing natural gas well was separated from a solvent by vacuum distillation. The mixture contained 10- 15% by volume of a white crystalline solid which was rendered into a homogeneous liquid by the addition of hexane. The hexane solution of the diamondoids was then percolated through activated alumina. After removal of the hexane, the mixture of diamondoid compounds was cooled in a dry ice/acetone bath for 24 hours and then transferred into a glove bag using a pre-cooled Buchner funnel. The temperature of the mixture in the Buchner funnel was -60°C at the beginning of the filtration and -40"C at the end of the filtration. Fuel properties of the liquid filtrate are shown in Table 2.
  • Figure 1 shows a Simdis chromatograph (ASTM Designation D 2887-84) of the vacuum distilled diamondoid mixture of Examples I and II and Table 3 summarizes the Simdis boiling range of the mixture.
  • Example II The fuel described in Example 1 was hydrogenated over Ni on Kieselguhr at 230"C overnight. The product was filtered and evaluated as high density fuel. The sulfur content was reduced to 0.002% by weight while the other properties remained unchanged, as summarized in Table 2.
  • Figure 1 shows a Simdis chromatograph (ASTM Designation D 2887-84) of the vacuum distilled diamondoid mixture of Examples I and II and Table 3 summarizes the Simdis boiling range of the mixture.
  • Example III The mixture of diamondoid compounds as used in Example 1 was equilibrated in a centrifuge maintained at a constant temperature of -20°C for 72 hours, and the solid part of the mixture was centrifuged off. The liquid was found to have an API gravity of 20.9, a sulfur content of 0.096% by weight, and a net heat of combustion of 44.2 megajoules per kilogram, or 41.0 megajoules per liter. These results are summarized below in Table 2.
  • Figure 2 shows a Simdis chromatograph of the liquid portion of the centrifuged diamondoid mixture of Example III and Table 3 summarizes the Simdis boiling range of the mixture.
  • Example IV The mixture of diamondoid compounds as used in Example 1 was distilled without a column under vacuum.
  • the first fraction which came over as a solid at 25-40"C and 0.5 torr was essentially adamantane.
  • the second fraction which came over as a colorless liquid at 75-125°C and 0.5 torr was a complex mixture of essentially methylated adamantanes.
  • the colorless liquid fraction was evaluated as high density fuel, and was found to have a freezing point of ⁇ 50°C, an API gravity of 22.5, a sulfur content of 0.076% by weight, and a net heat of combustion of 42.4 megajoules per kilogram or 39.1 megajoules per liter. These results are shown below in Table 2.
  • Figure 3 shows a Simdis chromatograph of the high density fuel mixture of Example IV and Table 3 summarizes the Simdis boiling range of the mixture.
  • Example V A mixture of diamondoid compounds was recovered from a diamondoid-containing natural gas well as a liquid. The mixture of diamondoid compounds was tan in color and contained solid contaminants. The mixture was percolated through freshly calcined high activity gamma-alumina at room temperature.
  • FIG. 1 shows a Simdis chromatograph of the naturally occurring liquid diamondoid mixture of Example V and Table 3 summarizes the Simdis boiling range of the mixture.
  • the sample of Example V contained about 78 weight percent of diamondoid compounds having more than one quaternary carbon atom per molecule.
  • Example VI A mixture of diamondoid compounds was recovered from a diamondoid-containing natural gas well and separated from a solvent by distillation. The separated diamondoid mixture was found to contain 0.37% sulfur by weight. The mixture was then hydrotreated over a commercial Co-Mo/Al 2 0 3 catalyst. The treated diamondoid mixture was evaluated as a high density fuel without further modification. The mixture contained, at room temperature, approximately 10- 15% by volume of a white crystalline solid at the bottom and the rest was a clear liquid. The solid components dissolved into the liquid at «60°C, although the mixture contain solids, it was readily pourable at low temperatures. The pour point of the mixture was determined to be -4°C. Missile fuel properties of this mixture are shown in Table 2.
  • Figure 5 shows a Simdis chromatograph of the hydrotreated diamondoid mixture of Example VI and Table 3 summarizes the Simdis boiling range of the mixture.
  • the sample of Example VI contained about 36 weight percent of diamondoid compounds having more than one quaternary carbon atom per molecule.
  • Example VII A mixture of diamondoid compounds containing 75% by weight of the diamondoid mixture of Example I and separated from a solvent by vacuum distillation used in Example VI, and 25% by weight of the diamondoid mixture of Example V was made and evaluated as a high density fuel. This mixture contained approximately 10% by volume of white crystalline solids at room temperature and had a pour point of -114°C. Fuel properties of this mixture are shown in Table 2.
  • Figure 6 shows a Simdis chromatograph of the diamondoid mixture of Example VII and Table 3 summarizes the Simdis boiling range of the mixture. The sample of
  • Example VII contained about 39 weight percent of diamondoid compounds having more than one quaternary carbon atom per molecule.
  • Example VIII A mixture of diamondoid compounds contained 50% by weight of the diamondoid mixture used in Example VI, and 50% by weight of the diamondoid mixture used in Example V was made and evaluated as a high density fuel. The mixture contained approximately 5% by volume of a white crystalline solid at room temperature and had a pour point of -120°C. Missile fuel properties of this mixture are shown in Table 2.
  • Figure 7 shows a Simdis chromatograph of the diamondoid mixture of Example VIII and Table 3 summarizes the Simdis boiling range of the mixture.
  • the sample of Example VIII contained about 52 weight percent of diamondoid compounds having more than one quaternary carbon atom per molecule.
  • Example IX A mixture of diamondoid compounds containing 25% by weight of the diamondoid mixture used in Example VI, and 75% by weight of the diamondoid mixture in Example V, was evaluated as a high density fuel. This mixture was clear at room temperature and had a pour point of -105°C. The properties of this mixture are shown in Table 2.
  • Figure 8 shows a Simdis chromatograph of the diamondoid mixture of Example IX and Table 3 summarizes the Simdis boiling range of the mixture.
  • the sample of Example IX contained about 65 weight percent of diamondoid compounds having more than one quaternary carbon atom per molecule.
  • Table 2 shows the properties of the mixtures of Examples I-IX.
  • Jet A The properties of a jet fuel blending component designated as "Jet A" are presented for comparison.
  • Example X the diamondoid-containing mixtures produced by the process of the present invention exhibit higher energy densities than required for military jet fuel.
  • Example X the diamondoid-containing mixtures produced by the process of the present invention exhibit higher energy densities than required for military jet fuel.
  • a normally liquid diamondoid sample was transferred into a clear container with a faucet at the bottom.
  • the natural gas well which produced this normally liquid diamondoid sample required no solvent injection and the normally liquid diamonoid sample was recovered neat.
  • the aqueous and oil phases were clearly separated in this sample.
  • the aqueous phase was drained from the container and discarded.
  • the oil phase which was colored pale yellow, was percolated through a column of activated alumina (EM Science No. AX 0612-3, chromatographic grade, 80-200 mesh, ALCOA Type F-20) to a clear water-white liquid.
  • the composition and properties of this clear mixture are given in Column 4 of Table 2.
  • Figure 9 is a GC trace of the mixture using a capillary Column (Supelco Inc., SPB-1, 0.32 ID, 60 M, 1.0 urn).
  • the mixture was found to contain 6.5% of hydrocarbons boiling lower than adamantane and a good deal of these pre-adamantane materials were extremely low-boiling. The low flash point was attributed to the very low boiling components.
  • This diamondoid mixture was also found to contain 481 mg/liter extremely high boiling material which was initially classified as "existent gum", but which, upon further analysis, was found to contain high molecular weight diamondoids such as pentamantane.
  • the mixture had a high net heat of combustion per volume (146,894 Btu/gallon) and also had good low temperature properties. The properties of this mixture are summarized below in Table 4 together with JP-10 and RJ-5 missile fuel specifications for comparison.
  • Example XI The clear mixture obtained in Example X was subjected to a short-path distillation in a Kugelrohr apparatus. The total mixture was distilled at a pot temperature of 150"C and a vacuum of 4.0 torr. The low boilers were collected in a dry ice/acetone trap which was placed after the receiver (cooled by being partially immersed into a dry ice/acetone bath) for the diamondoids. Some residue (pentamantanes) remained in the pot. The composition and properties of the resulting diamondoids are given in Column 1 of Table 5. The GC results of the distilled mixture is given in Figure 10, and the composition and properties of the distilled mixture are also shown in Table 5. It is indicated that both the low boilers and the residue were removed by this simple operation.
  • Example XII One liter of the clear diamondoids obtained in Example X was purged with a nitrogen stream at room temperature at a rate of 20CC/min. The nitrogen outlet was passed through a dry ice/acetone cold trap. After an hour, the operation was stopped. Most, but not all, of the low boilers were removed into the cold trap. The GC results of the remaining diamondoids are shown in Figure 11. The properties and the compositions are given in Column 2 of Table 5. The flash point was raised considerably to 62.8°C. TABLE 5
  • Example XI Example XII Short-Path Nitrogen
  • Example XIII A portion of the crude diamondoid sample of Example X was transferred from storage to a clear container with a faucet at the bottom. The aqueous phase was drained. The oil phase was dried over anhydrous sodium sulfate. The dried oil phase was subjected to a short-path distillation at a pot temperature of 150"C, a vacuum of 5 torr. The low boilers were collected in a dry ice/acetone trap, and the diamondoids were collected in the receiver at room temperature. Essentially, the same results were obtained as in Example XI.
  • Example XIV shows that the process of the present invention can readily convert a naturally occurring mixture of diamondoids to a high density fuel by one simple short-path distillation, even without first percolating through activated alumina as described in Example X. Further, the process does not require impractically high vacuum, nor does it require expensive refrigeration of the receiver for the diamondoids.
  • Example XIV shows that the process of the present invention can readily convert a naturally occurring mixture of diamondoids to a high density fuel by one simple short-path distillation, even without first percolating through activated alumina as described in Example X. Further, the process does not require impractically high vacuum, nor does it require expensive refrigeration of the receiver for the diamondoids.
  • Example XIV shows that the process of the present invention can readily convert a naturally occurring mixture of diamondoids to a high density fuel by one simple short-path distillation, even without first percolating through activated alumina as described in Example X. Further, the process does not require impractically high vacuum, nor does it require expensive refrigeration of the receiver for the diamond
  • Example X The diamondoids cleaned up as described in Example X were fractionated into (1) low boilers, (2) adamantanes, (3) diamantanes, (4) triamantanes + tetramantanes + pentamantanes.
  • the composition and properties of each fraction are given in Table 6.
  • Figure 12 shows the GC results of the fractions.
  • Examples XV - XVIII show that the diamondoid-containing fractions produced in accordance with the present invention can be blended to formulate useful energy density-enhancing additives.
  • the fraction containing triamantanes and tetramantanes was found to have the highest density and the highest heat of combustion per volume.
  • the following Examples show that the desirable qualities of high heat density can be combined with good low temperature properties by blending the fraction containing triamantanes and tetramantanes with single compounds such as cyclohexane.
  • Example XV A blend was made by mixing 75 wt% of the diamondoid mixture of Example X and 25 wt% of Fraction (3) prepared in Example XIV. The composition and properties are shown in Column 1 of Table 7. The addition of this amount of diamantanes to the total mixture increased the heat of combustion per volume, and retained the good low temperature properties.
  • Example XVI A blend was made by mixing 50 wt% of the diamondoid mixture of Example X and 50 wt% of Fraction (3) of Example XIV. The composition and properties are shown in Column 2 of Table 7.
  • Example XVII A blend was made by mixing 92.5 wt% of the diamondoid mixture of Example XIII and 7.5 wt% of cyclohexane. Results are shown in Table 8.
  • Example XVIII A blend was made by mixing 45 wt% of the diamondoid mixture of Example I, purified as described in Example IV, 45 wt% of Fraction (3) , the diamantanes, prepared in Example V, and 10 wt% of cyclohexane. Results are shown in Table 8. TABLE 7 Properties of Diamondoid Blends
  • Example XIX The diamondoids cleaned up as described in Example X were fractionally distilled to remove the fractions of low boilers and adamantanes, leaving the diamantanes, triamantanes and higher homologues in the pot.
  • the pale- yellow liquid in the pot was percolated through activated alumina to obtain a water-white material of excellent missile fuel properties.
  • the composition and properties of this material is given in Column 1 of Table 9.
  • Example XX A mixture was made of 90 wt % of the diamondoids obtained in Example XIX and 10 wt % of cyclohexane. The composition and properties are shown in Column 2 of Table 9. The low temperature viscosities have been lowered from Example XIX by the addition of cyclohexane.
  • Example XXI and XXII A mixture was made of 50 wt % of diamondoid Fraction 3 obtained in Example XIV and 50 wt % of a commercially available jet fuel Jet A which is used to formulate JP-8.
  • the composition and properties of the commercial jet fuel are shown in Column 1 of Table 10 as Example XXI, while the composition and properties of the diamondoid-enhanced jet fuel mixture are shown in Column 2 of Table 10 as Example XXII. TABLE 10 Properties of Examples XXI and XXII
  • a No. 6 diesel fuel was injected into the surface equipment of an operating natural gas field to solve the diamondoid plugging problem according to U.S. 4,982,049. After the diesel fuel was saturated with the diamondoids, the diamondoid-saturated mixture was withdrawn from the surface equipment and percolated through activated alumina to remove any corrosion inhibitors used to prevent corrosion of the equipment. The net heat of combustion of the cleaned up diamondoid saturated No. 6 diesel fuel was found to have increased by 5,439 Btu/Gallon from the injected No. 6 diesel fuel while the low temperature properties were also improved.
  • the properties of the No. 6 diesel are shown in Table 11 as Example XXIII, while the properties of the diamondoid saturated No. 6 diesel are shown in Table 11 as Example XXIV. TABLE 11 Properties of Examples XXIII and XXIV

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé permettant d'accroître la densité énergétique de carburants Diesel et de carburants pour avions, par adjonction de constituants diamantoïdes de densité énergétique extrêmement élevée. Ces constituants diamantoïdes comprennent une composition ayant subi un traitement visant à enlever au moins une part de composés organiques comportant moins de 10 atomes de carbone. Ladite composition comprend au moins environ 65 % en poids de composés diamantoïdes substitués par alkyle, qui contiennent plus d'un atome de carbone quaternaire par molécule et moins d'environ 35 % en poids de composés diamantoïdes comportant moins de deux atomes de carbone quaternaire par molécule. Les composés diamantoïdes substitués par alkyle comprennent des adamantanes, des diamantanes, des triamantanes et des tétramantanes. Les additifs selon l'invention augmentent la densité énergétique d'un carburant constitué d'un distillat moyen tout en améliorant le mélange obtenu en ce qui concerne son point de congélation et ses points d'écoulement ou en maintenant lesdits points au niveau désiré. L'invention concerne également des procédés permettant de préparer ladite composition et de faire fonctionner des moteurs à combustion.
PCT/US1994/009960 1993-10-28 1994-09-02 Distillats moyens constituant des carburants a haut rendement Ceased WO1995011873A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU78308/94A AU7830894A (en) 1993-10-28 1994-09-02 High performance middle distillate fuels

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14204093A 1993-10-28 1993-10-28
US08/142,040 1993-10-28

Publications (1)

Publication Number Publication Date
WO1995011873A1 true WO1995011873A1 (fr) 1995-05-04

Family

ID=22498338

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/009960 Ceased WO1995011873A1 (fr) 1993-10-28 1994-09-02 Distillats moyens constituant des carburants a haut rendement

Country Status (2)

Country Link
AU (1) AU7830894A (fr)
WO (1) WO1995011873A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5922175A (en) * 1997-02-04 1999-07-13 Elf Atochem S.A. Purification of chlorotetraflouroethane by extractive distillation
CN109797015A (zh) * 2019-01-29 2019-05-24 天津大学 一种含有烷基十氢萘和烷基金刚烃的燃料、其制备方法及用途

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3646233A (en) * 1969-11-14 1972-02-29 Sun Oil Co Reaction of paraffins with adamantane compounds
US4022845A (en) * 1976-05-28 1977-05-10 Idemitsu, Kosan Kabushiki-Kaisha (Idemitsu Kosan Co., Ltd.) Process for producing alkyl adamantanes
EP0078998A2 (fr) * 1981-11-06 1983-05-18 BASF Aktiengesellschaft Combustible hydrocarboné liquide contenant du polyisobutylène et son utilisation dans des turbines à gaz d'aviation
SU915407A1 (en) * 1980-10-23 1985-01-15 Inst Neftechimicheskogo Sintez Method of obtaining mixture of mono- and poly-methyladamantanes
US4717465A (en) * 1984-12-31 1988-01-05 Mobil Oil Corporation Process for producing jet fuel with ZSM-22 containing catalist
US4804795A (en) * 1985-12-05 1989-02-14 Nippon Oil Co., Ltd. High-density fuel oil
US4943302A (en) * 1988-10-14 1990-07-24 Enichem Synthesis S.P.A. Fuel composition with a high energy content
US4952749A (en) * 1989-05-26 1990-08-28 Mobil Oil Corp. Removal of diamondoid compounds from hydrocarbonaceous fractions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3646233A (en) * 1969-11-14 1972-02-29 Sun Oil Co Reaction of paraffins with adamantane compounds
US4022845A (en) * 1976-05-28 1977-05-10 Idemitsu, Kosan Kabushiki-Kaisha (Idemitsu Kosan Co., Ltd.) Process for producing alkyl adamantanes
SU915407A1 (en) * 1980-10-23 1985-01-15 Inst Neftechimicheskogo Sintez Method of obtaining mixture of mono- and poly-methyladamantanes
EP0078998A2 (fr) * 1981-11-06 1983-05-18 BASF Aktiengesellschaft Combustible hydrocarboné liquide contenant du polyisobutylène et son utilisation dans des turbines à gaz d'aviation
US4717465A (en) * 1984-12-31 1988-01-05 Mobil Oil Corporation Process for producing jet fuel with ZSM-22 containing catalist
US4804795A (en) * 1985-12-05 1989-02-14 Nippon Oil Co., Ltd. High-density fuel oil
US4943302A (en) * 1988-10-14 1990-07-24 Enichem Synthesis S.P.A. Fuel composition with a high energy content
US4952749A (en) * 1989-05-26 1990-08-28 Mobil Oil Corp. Removal of diamondoid compounds from hydrocarbonaceous fractions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5922175A (en) * 1997-02-04 1999-07-13 Elf Atochem S.A. Purification of chlorotetraflouroethane by extractive distillation
CN109797015A (zh) * 2019-01-29 2019-05-24 天津大学 一种含有烷基十氢萘和烷基金刚烃的燃料、其制备方法及用途

Also Published As

Publication number Publication date
AU7830894A (en) 1995-05-22

Similar Documents

Publication Publication Date Title
US4097367A (en) Conversion of olefinic naphtha
KR970001190B1 (ko) 윤활 베이스 오일 및 그 제조 방법
US4211640A (en) Process for the treatment of olefinic gasoline
CA1110192A (fr) Production d'huiles speciales
MXPA97001763A (en) Gasol improvement process
KR100351598B1 (ko) 가솔린개량방법
EP0056718B1 (fr) Prétraitement de charges pour la conversion catalytique
US4413153A (en) Integrated process for making transportation fuels and lubes from wet natural gas
US5500108A (en) Gasoline upgrading process
JP3011782B2 (ja) 水素化分解原料油からの変圧器油組成物の製造法
WO2010122115A2 (fr) Valorisation de naphtas légers pour une production d'oléfines augmentée
US2749225A (en) Process for producing a hydrocarbon fuel
US4071574A (en) Conversion of Fischer-Tropsch heavy product to high quality jet fuel
EP0057980A1 (fr) Prétraitement de charges pour le déparaffinage catalytique
EP3237581B1 (fr) Procédé de production d'hydrocarbures c2 et c3
US5401389A (en) Gasoline-cycle oil upgrading process
EP0057071B1 (fr) Prétraitement de charges pour le déparaffinage catalytique
US4310409A (en) Thermal cracking of heavy fraction of hydrocarbon hydrogenate
US5352354A (en) Gasoline upgrading process
US4483760A (en) Process for dewaxing middle distillates
US4044064A (en) Conversion of Fischer-Tropsch heavy product to high quality jet fuel
CN108795514B (zh) 一种吸热型航空燃料及其制备方法
WO1995011873A1 (fr) Distillats moyens constituant des carburants a haut rendement
EP3237583B1 (fr) Procédé de production de gpl et btx
EP1599563A2 (fr) Procede pour la production de l'essence a indice d'octane recherche (ior) eleve utilisant une zeolithe cfi

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase