Process for Converting C2-C7 Olefins into Fuel

This application claims priority to U.S. Provisional Patent Application Nos. 63/432,650 and 63/459,523 filed on Dec. 14, 2022 and Apr. 14, 2023, respectively, each entitled “Two-Step Process for Transformation of Ethanol into Jet Fuel and/or Diesel Fuel,” and U.S. Provisional Patent Application No. 63/530,408 filed on Aug. 2, 2023, entitled “PROCESS FOR CONVERTING C-COLEFINS INTO FUEL,” the disclosures of which are incorporated herein by reference in their entirety.

The subject matter described herein relates to a process for converting one or more C-Clinear or branched olefins to fuel (e.g., one or more C-Chydrocarbons).

Traditionally, petroleum is used as the starting point for the synthesis of fuels. For example, the oligomerization of light gaseous mono-olefins to form gasoline or diesel type hydrocarbons has been carried out by using acid catalysts such as supported phosphoric acid, and olefin dimers have been generally obtained for gasoline additives after hydrogenation of the dimers. Olefin trimerization has been mainly carried out by using solid acid catalysts, such as heteropoly acid, zirconium, zeolites, amorphous silica alumina and sulfated titania. Ionic liquids are also used for these reactions. However, these catalyst compositions can be expensive and can result in low yields. Moreover, these processes produce oligomers in a non-selective manner by the oligomerization of C-Colefins, which typically generate a mathematical distribution (Schulz-Flory or Poisson) of oligomers, which often does not match market demand.

Nickel-based heterogeneous catalysts have also been used for ethylene oligomerization to provide mixtures of C-Colefins, which are secondarily oligomerized to C-Colefins. While these catalysts may be less expensive, the major products of these reactions are lower carbon number olefins and hydrocarbons, and not primarily Coligomers, which is required for efficient production of renewable jet or diesel fuel.

In other implementations, processes have been reported that utilize cation exchange resins for oligomerizing isobutene and other light olefins derived from petroleum to jet fuel range oligomers. Tetramers or pentamers could also be obtained by the oligomerization of pre-formed dimers with ion exchange resins. Moreover, an ion exchange resin, Amberlyst-15, has been used in the oligomerization of light olefins. Similarly, Amberlyst-35 ion exchange resin affords higher levels of trimers, but dimers are present at 30-40% mass yield, which can ultimately decrease the amount of jet and diesel fuel production, thereby increasing cost.

Accordingly, there remains a need for improved catalyst technologies that result in greater yields to fuels from light gaseous mono-olefins (e.g., C-C).

Aspects of the current subject matter relate to process for converting one or more C-Clinear or branched olefins to one or more C-Chydrocarbons. In some implementations, one or more of the following features may optionally be included in any feasible combination.

In one implementation, an exemplary process for converting one or more C-Clinear or branched olefins to one or more C-Chydrocarbons can include contacting a feed stream that includes the one or more C-Clinear or branched olefins with one or more catalysts in a reactor at a temperature from about 100° C. to 400° C., a pressure from about 200 psig to 1000 psig, and a weight hourly space velocity (WHSV) of at least 0.5 hto form a mixture. The mixture includes one or more C-Chydrocarbons at a yield of at least 30%; and the one or more catalysts include a doped mixed metal oxide.

In some implementations, the doped metal oxide can include one or more dopants. The one or more dopants can include nickel, cobalt, yttrium, rhodium, ruthenium, palladium, platinum, ion, lanthanum, silica, alumina, scandium, titanium, niobium, copper, chromium, rhenium, zinc, vanadium, iridium, or any combination thereof. In certain implementations, the nickel can be present in an amount that is from about 0.5 weight percent to 5 weight percent of the one or more catalysts.

In some implementations, the doped mixed metal oxide can include tungsten, zirconium, molybdenum, silica, alumina, or any combination thereof. The tungsten can be present in an amount that is from about 5 weight percent to 25 weight percent of the one or more catalysts.

In another implementation, an exemplary process for converting one or more C-Clinear or branched olefins to one or more C-Chydrocarbons, the process can include contacting a feed stream that includes the one or more C-Clinear or branched olefins with one or more catalysts in a reactor at a temperature from about 100° C. to 400° C., a pressure from about 200 psig to 1000 psig, and a weight hourly space velocity (WHSV) of at least 0.5 hto form a mixture. The mixture includes the one or more C-Chydrocarbons at a yield of at least 30% and the one or more catalysts includes a first catalyst. The first catalyst can include nickel doped tungstated zirconium, nickel doped tungstated γ-alumina, nickel doped tungstated silica, nickel doped amorphous silica alumina, or nickel doped zeolite.

In some implementations, the reactor can be a single bed reactor. The single bed reactor can be a fixed bed reactor or a fluidized bed reactor.

In some implementations, the reactor can be a stacked bed reactor.

In some implementations, nickel can be present in an amount that is from about 0.5 weight percent to 5 weight percent of the first catalyst.

In some implementations, tungsten can be present in an amount that is from about 5 weight percent to 25 weight percent of the first catalyst.

In some implementations, the first catalyst includes nickel doped tungstated zirconium.

In some implementations, the one or more catalysts can further include a second catalyst. The second catalyst can include one or more zeolites or one or more solid acids, or a combination thereof. In some implementations, the one or more solid acids can include one or more sulfonic resins.

In some implementations, the one or more zeolites can include one or more doped zeolites.

In some implementations, the one or more C-Chydrocarbons can include one or more C-Chydrocarbons.

In some implementations, the one or more C-Chydrocarbons can include one or more C-Chydrocarbons.

In some implementations, the feed stream can further include a fusel oil, a residual alcohol, corn oil, water, or any combination thereof. The water can be present in the feed stream in an amount of less than 20 ppm.

In some implementations, the process can further include a recycle stream that can include a portion of the one or more C-Chydrocarbons of the mixture.

In some implementations, the one or more C-Clinear or branched olefins can include ethylene, propylene, butene, pentene, hexene, or any combination thereof.

In some implementations, the process can further include preparing the feed stream, which can include contacting an input stream with one or more catalysts in one or more reactors to form the one or more C-Clinear or branched olefins. The input stream can include one or more C-Clinear or branched alcohols. The one or more C-Clinear or branched alcohols can include ethanol, propanol, butanol, or any combination thereof.

In some implementations, the one or more catalysts can include a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium, titanium, tungsten, or silicon. In some implementations, the one or more catalysts can include a doped or undoped zeolite catalyst.

In some implementations, the process can further include preparing the feed stream, which can include deriving the one or more C-Clinear or branched olefins from petroleum.

In some implementations, the process can further include recycling a portion of the one or more C-Chydrocarbons present in the mixture into the feed stream.

In some implementations, the process can further include hydrogenating the one or more C-Chydrocarbons to produce a product stream.

In some implementations, the process can further include recycling a portion of the one or more C-Chydrocarbons present in the product stream into the feed stream.

In some implementations, the process can further include separating the one or more C-Chydrocarbons from the product stream to produce a renewable jet fuel or a renewable diesel fuel. In some implementations, the process can further include blending the renewable jet fuel with an aromatic compound or a fossil-fuel derived compound. In some implementations, the process can further include blending the renewable diesel fuel with an aromatic compound or a fossil-fuel derived compound.

In some implementations, the yield of the one or more C-Chydrocarbons can be from about 30% to 99%.

In some implementations, the yield of the one or more C-Chydrocarbons can be at least about 45%.

In some implementations, the yield of the one or more C-Chydrocarbons can be at least about 65%.

In some implementations, the yield of the one or more C-Chydrocarbons can be at least about 80%.

In some implementations, the pressure can be from about 400 psig to 700 psig or from about 600 psig to 800 psig.

In some implementations, the temperature can be from about 150° C. to 300° C.

In some implementations, the weight hourly space velocity (WHSV) can be from about 1 hto about 10 hor from about 1 hto about 5 h.

In another implementation, an exemplary process for converting one or more C-Clinear or branched olefins to one or more C-Chydrocarbons can include contacting a feed stream that includes the one or more C-Clinear or branched olefins with one or more catalysts in a reactor at a temperature from about 250° C. to 350° C., a pressure from about 400 psig to 700 psig, and a weight hourly space velocity (WHSV) of at least 2 hto form a mixture. The mixture includes one or more C-Chydrocarbons at a yield of at least 40% and the one or more catalysts comprise nickel doped tungstated zirconium.

In another implementation, an exemplary for converting one or more C-Clinear or branched olefins into jet fuel or diesel fuel can include forming, via a single oligomerization step, one or more one or more C-Chydrocarbons. The single oligomerization step includes contacting a feed stream comprising the one or more C-Clinear or branched olefins with one or more catalysts in a reactor at a temperature from about 100° C. to 400° C., a pressure from about 200 psig to 1000 psig, and a weight hourly space velocity (WHSV) of at least 0.5 hto form a mixture The mixture includes the one or more C-Chydrocarbons at a yield of at least 30% and the one or more catalysts comprise a first catalyst, the first catalyst comprising nickel doped tungstated zirconium, nickel doped tungstated γ-alumina, nickel doped tungstated silica, nickel doped amorphous silica alumina, or nickel doped zeolite.

In some implementations, the process can further include hydrogenating the one or more C-Chydrocarbons to produce a product stream.

In some implementations, the process can further include recycling a portion of the one or more C-Chydrocarbons present in the product stream into the feed stream.

In some implementations, the process can further include separating the one or more C-Chydrocarbons from the product stream to produce the renewable jet fuel or the renewable diesel fuel.

In some implementations, the process can further include blending the renewable jet fuel with an aromatic compound or a fossil-fuel derived compound.

In some implementations, nickel can be present in an amount that is from about 0.5 weight percent to 5 weight percent of the first catalyst.

The some implementations, tungsten can be present in an amount that is from about 5 weight percent to 25 weight percent of the first catalyst.

In some implementations, the one or more catalysts further include a second catalyst. The second catalyst can include one or more zeolites or one or more solid acids, or a combination thereof.

In some implementations, the process can further include recycling a portion of the one or more C-Chydrocarbons present in the mixture into the feed stream.

In some implementations, the one or more the one or more C-Clinear or branched olefins can be derived from C-Cmonohydric alcohols.

In some implementations, the one or more C-Chydrocarbons can include one or more low carbon intensity C-Chydrocarbons.

In some implementations, the one or more C-Chydrocarbons can include one or more zero carbon intensity C-Chydrocarbons.