STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0001] The invention described herein may be manufactured and used by or for the government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

FIELD OF THE INVENTION

[0002] The invention generally relates to processes for converting alcohol feedstocks to diesel/turbine fuels, and more specifically, using catalytic methods to efficiently convert biofeedstocks into diesel/turbine fuels.

SUMMARY

[0003] In accordance with one aspect of the invention, a process for manufacturing turbine and/or diesel fuels is provided. The process includes providing an alcohol feedstock that includes at least one alcohol. The alcohol is dehydrated with at least one solid catalyst at a temperature ranging from 200 °C to 400 °C to produce an olefin mixture. The mixture is oligomerized directly with at least one metallocene-based Ziegler Natta catalyst and a methylaluminoxane (MAO) cocatalyst to produce an oligomer mixture that includes oligomers and unreacted olefins. An isomerization catalyst is introduced to the oligomer mixture to produce, in situ, a bimetallic isomerization/oligomerization catalyst which converts the unreacted olefins to oligomers through 1,2-addition. The process further includes hydrogenating and distilling the oligomers to produce a fully saturated diesel or turbine fuel.

[0004] In some embodiments, the alcohol can be selected from the group consisting of single alcohols, mixed alcohols, and complex mixtures including alcohols. The alcohol can be selected from the group having a formula C _n H(2 _n +i)-x(OH) _x , where n and x are real integers greater than or equal to one. The alcohol may be a Ci-Cio alcohol, such as methanol, ethanol, propanol, butanol,

i pentanol, combinations thereof, and the like.

[0005] The olefin mixture can include at least 5 wt. %, or at least 10 wt. %, or at least 20 wt. %, or at least 40 wt. %, or at least 80 wt. % primary olefins, and can be up to 100 wt. %, or up to 90 wt. % primary olefins. The olefin mixture can be 20-80 wt. % primary olefins, which is considered moderately rich in primary olefins. The alcohol feedstock can be greater than 80 wt. % primary olefins, which is considered rich in primary olefins.

[0006] The alcohol feedstock can contain less than 20% primary olefins.

[0007] The alcohol feedstock can include a total of at least about 10 wt. %, or at least about 20 wt. %, or at least 40 wt. %, or at least 80 wt. % of the at least one alcohol and can be up to 90% or up to 100% alcohol.

[0008] The isomerization catalyst can include/be at least one Lewis acid that promotes isomerization without affecting the oligomerization process. The isomerization catalyst can include at least one metal selected from nickel, platinum, palladium, and combinations thereof. The isomerization catalyst can include a transition metal with the metal in the +2 to +6 oxidation state which is selected from Ni, Zn, Pd, Pt, Cr, Cr, Fe, Fe, Mn, Co, and combinations thereof. The isomerization catalyst can include at least one ligand, attached to the metal.

[0009] The bimetallic catalyst can have a Lewis acid:metallocene ratio ranging from 0.1 to 10, by weight, or 0.5 to 2, by weight.

[0010] The metallocene based Ziegler Natta catalyst and the methylaluminoxane (MAO) cocatalyst can have/be prepared with a molar ratio of Al:Zr of from 1 :1 to 1000: 1 , or from 1 :1 to 100: 1.

[0011] The dehydration catalyst can be a heterogeneous catalyst. The dehydration catalyst can be selected from gamma alumina, transition metal oxides, aluminum phosphate, and other heterogeneous catalysts having moderate acidity.

[0012] The olefin mixture can include at least one of 1-butene and 2-butene. The unreacted olefin can include an internal olefin, i.e., an olefin which is saturated at the beta or higher position. The internal olefin can include/be 2-butene. The oligomers can include a chain derived from 1-butene. The forming of oligomers through 1,2-addition can include forming butene oligomers through 1,2- addition. In some embodiments, the process includes separating the unreacted olefins by temperature controlled distillation. [0013] In various aspects the oligomerizing of the mixture and the introducing an isomerization catalyst can be performed in a one step process which includes oligomerizing the mixture with at least one bimetallic isomerization/oligomerization catalyst having a metallocene based catalyst in conjunction with an isomerization catalyst to produce oligomers formed through 1,2-addition.

[0014] In another embodiment of the invention, a process for manufacturing turbine and/or diesel fuels includes providing an alcohol feedstock comprising at least one alcohol, dehydrating the at least one alcohol with at least one solid acid catalyst at temperatures ranging from 200 °C to 400 °C to produce an olefin mixture, and, in a one step process, oligomerizing the mixture with at least one bimetallic isomerization/oligomerization catalyst having a metallocene based catalyst in conjunction with an isomerization catalyst to produce oligomers formed through 1,2-addition.

[0015] The process can further include hydrogenating and distilling the oligomers to produce fully saturated diesel and turbine fuels.

[0016] The process can be further characterized as for the process described above.

[0017] In another aspect, a process for manufacturing turbine and/or diesel fuels includes providing an alcohol feedstock, dehydrating the alcohol in the feedstock with at least one solid catalyst at temperatures ranging from 200 °C to 400 °C to produce an olefin mixture, oligomizering the mixture directly with at least one metallocene based Ziegler Natta catalyst and methylaluminoxane (MAO) cocatalyst to produce an oligomer mixture including unreacted internal olefins and oligomers, separating the unreacted olefins by temperature controlled distillation, converting the unreacted olefins to a distribution of oligomers with a bimetallic isomerization/oligomerization catalyst having a metallocene based catalyst in conjunction with an isomerization catalyst to produce oligomers formed through 1,2-addition, and hydrogenating and distilling the oligomers to produce fully saturated diesel and turbine fuels.

[0018] The process can be further characterized as for the processes described above.

BRIEF DESCRIPTION OF THE DRAWING

[0019] FIG. 1 is a generic diagram for the conversion of mixed olefin feedstocks to turbine and diesel fuels, according to embodiments of the invention. [0020] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not to be viewed as being restrictive of the invention, as claimed. Further advantages of this invention will be apparent after a review of the following detailed description of the disclosed embodiments, which are illustrated schematically in the accompanying drawings and in the appended claims.

DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION

[0021] Embodiments of the invention generally relate to processes for converting alcohol feedstocks to diesel/turbine fuels.

[0022] Several technologies exist for the oligomerization of short chain olefins. Oligomerizations catalyzed by Ziegler Natta catalysts have been shown to result in desired distributions of isomers. One drawback of this approach is that these catalysts are only effective with primary olefins. The use of a bimetallic catalyst system to isomerize internal olefins with concomitant conversion of primary olefins to oligomers allows for efficient conversion of mixed olefin feedstocks to fuels suitable for both jet and diesel propulsion.

[0023] The fermentation of sugars derived from biomass to alcohols is a proven and effective method for the conversion of sustainable feedstocks to fuels. Although fuels such as ethanol, n- butanol and more recently, n-pentanol have utility as gasoline replacements, certain applications (e.g. jet aircraft propulsion, military vehicles) require fully saturated hydrocarbon fuels. Alcohols can be dehydrated to olefins with modest energy inputs and the olefins can subsequently be oligomerized to produce saturated fuels. The use of specific Ziegler Natta catalysts under controlled conditions has been shown to be an effective route for conversion of primary olefins to jet fuels. In part, the suitability of such fuels is due to their well-controlled branching coupled with chain length selectivity. Dehydration of longer chain alcohols (e.g. C4-C20) typically produces a mixture of internal, external and branched chain olefins. To address this issue, embodiments of the invention combine an isomerization catalyst with the Ziegler-Natta oligomerization catalyst. The isomerization catalyst produces an equilibrium mixture of olefins including a significant amount of primary olefins. The Ziegler Natta catalyst can then convert the primary olefin to oligomer which then allows for the further conversion of remaining internal olefins. In summary, the synergistic effect of the bimetallic system allows for internal olefins to be effectively converted to specific distributions of oligomers.

[0024] Solid acid catalysts including, but not limited to, zeolites, cation exchange resins, polyphosphoric acid and aluminosilicate clays can effectively oligomerize mixed olefin feedstocks. These methods are in general far less selective than the current approach. An isomerization- polymerization catalyst based on a titanium trichloride-nickel ehloride-triethylaluminum catalyst has been described in the literature. Catalyst systems in embodiments of the invention do not produce high molecular weight polymer, but instead are selective for well-defined oligomer distributions.

[0025] Selective isomerization/oligomerization of olefin precursors allows for the custom synthesis of saturated, hydrocarbon fuels from renewable feedstocks. This in turn reduces the carbon footprint of the fuel production process without sacrificing vehicle performance.

[0026] Pure or mixed alcohol feedstocks (e.g. ethanol, propanols, butanols, pentanols...) are derived from renewable sources, and are subsequently dehydrated with a solid acid catalyst at elevated temperature, in the range between about 200 °C and about 400 °C. Potential catalysts include, but are not limited to; gamma alumina, transition metal oxides, aluminum phosphate, and other heterogeneous catalysts of modest acidity. In an embodiment, catalysts that produce mainly (>80%) primary olefins are utilized. In the case of alcohol feedstocks that only include internal alcohols, the choice of catalyst is dictated by overall conversion efficiencies and not by selectivity to primary olefins.

[0027] In embodiments, the mixed olefin feedstock can be converted to oligomers by two routes. When the feedstock is sufficiently rich in primary olefins (20-80%), or >80%, the olefins can be directly oligomerized by a metallocene based Ziegler Natta catalyst with methylaluminoxane (MAO) cocatalyst Al:Zr = 100:1 as described in US Patent Application Serial Number 12/511,796 which is hereby in its entirety incorporated by reference. This transformation results in the quantitative conversion of the normal olefins to an oligomer mixture, while internal olefins are untouched. The unreacted olefins can be separated by a low temperature distillation and then converted to a specific distribution of oligomers through the use of a bimetallic isomerization/oligomerization catalyst comprised of a metallocene based catalyst in conjunction with an isomerization catalyst.

[0028] In alternative embodiments, the isomerization catalyst can be added directly to the reaction mixture without separation. The isomerization catalyst can be selected from a list of modest Lewis acids that promote isomerization without affecting the oligomerization process. Examples include, but are not limited to transition metal catalysts based on; Ni(II), Zn(II), Pd(H), Pt(II), Cr(II), Cr(III), Fe(II), Fe(III), Mn(II), V(II), V(III), and Co(II). These catalysts can be added with or without ligands, typically with a Lewis Acid:metallocene ratio in the range of from about 0.1 to about 10, or alternatively from about 0.5 to about 2. The isomerization catalyst and oligomerization catalyst are slurried or dissolved in a non-coordinating solvent and are then activated with MAO. In embodiments, the isomerization/oligomerization reaction can be carried out at similar temperatures and pressures as the direct oligomerization process.

[0029] In another alternate embodiment, the approach that is particularly useful for olefin feedstocks with modest amounts of primary olefins (< -20%) is to forego the direct oligomerization and subject the original olefin mixture to the isomerization/oligomerization catalyst. Oligomerization mixtures are upgraded through hydrogenation and distillation as described in US patent application Serial Number 12/511,796 which is hereby in its entirety incorporated by reference to produce fuels suitable for use in turbine or diesel engines.

[0030] Example: C iZrCk and NiCl ₂ are added to a reactor and activated by addition of 100 molar equivalents of MAO in toluene. The solution is allowed to react for one hour and the solvent along with residual AlMe ₃ is removed under reduced pressure. Dry trans-2-butene is condensed onto the catalyst, the reactor is then sealed, and the solution is stirred for several hours at room temperature. The reaction is quenched with water, filtered, and the resultant distribution of oligomers is upgraded through hydrogenation and distillation.

[0031] Figure 1 illustrates a method for the conversion of alcohol feedstocks to fully saturated turbine and diesel fuels. In the initial step (SI 00), pure alcohols or mixtures are dehydrated to produce an olefin feedstock. This mixed feedstock can then be either directly oligomerized with an appropriate Ziegler Natta catalyst (SI 02) and any internal olefins oligomerized with a bimetallic isomerization/oligomerization catalyst, which can be produced in situ (SI 04). Or, depending on the distribution of olefins, the mixture of olefins can be isomerized and oligomerized with a bimetallic isomerization/oligomerization catalyst to produce a specific distribution of oligomers (SI 10). In the case of direct oligomerization, residual olefins are optionally separated by distillation (SI 12) and then subjected to isomerization/oligomerization conditions (SI 14) to further improve the yield of the process. Oligomer mixtures are then hydrogenated (SI 06) and distilled (SI 08) to produce fuels suitable for use in both turbine and diesel engines.

[0032] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.