# US 2025/0084331 A1 · Sustainable aviation fuel from normal alpha olefin byproducts and process for same

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- Number: US 2025/0084331 A1
- Document ID: US20250084331A1
- Status: Published application
- Kind: A1
- Application number: 18/462,558
- Filed: 2023-09-07
- Published: 2025-03-13
- Earliest claimed: 2023-09-07
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Michael S. Webster-Gardiner; James Hiller; Reza Khankal; Jared Fern
- Web page: https://patentgrep.com/patent/US20250084331A1

## CPC

- C10G 69/126: {polymerisation, e.g. oligomerisation}
- C10L 1/06: for spark ignition
- B01J 31/0267: {Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen}
- B01J 31/143: {of aluminium}
- B01J 31/34: of chromium, molybdenum or tungsten
- C07C 1/24: by elimination of water
- C07C 2/08: Catalytic processes
- C07C 2/32: as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)}
- C07C 5/03: of non-aromatic carbon-to-carbon double bonds
- C07C 6/04: at a carbon-to-carbon double bond
- C10G 3/42: {Catalytic treatment}
- C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- B01J 2231/20: Olefin oligomerisation or telomerisation
- C07C 2531/22: Organic complexes
- C07C 2531/24: Phosphines
- C10G 2300/1014: of vegetal origin
- C10G 2400/08: Jet fuel
- C10G 2400/22: Higher olefins
- C10L 2270/04: for turbines, planes, power generation
- Y02P 30/20: using bio-feedstock
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Process for making sustainable aviation fuel (SAF) from specific bio-ethylene oligomerization reactions producing a C4-C8 alpha-olefin and a by-product mixture of C10 olefins. This mixed decene stream is upgraded by further oligomerizing with at least one C4-C6 alpha-olefin to provide a C16− olefin stream, which is hydrogenated to C16− paraffins which is used to form a SAF. Employing bio-ethylene to produce the mixed decene stream, which is relatively low-value due in part to its non-selectivity, leverages that non-selectivity into a desirable sustainable aviation fuel product where the low selectivity is preferable. These and other embodiments and aspects are described herein.

## Claims

### Claim 1

A process for making a sustainable aviation fuel, the process comprising:
(a) providing a bio-ethylene feed, at least a portion of which is derived from the dehydration of biomass ethanol;
(b) contacting the bio-ethylene feed with a first catalyst system comprising a first oligomerization catalyst to form an oligomerization product comprising at least one C4-C8 alpha-olefin and a mixture of decenes;
(c) separating the mixture of decenes from the oligomerization product;
(d) (i) contacting the mixture of decenes with at least one C6− alpha-olefin in the presence of a second catalyst system comprising a second oligomerization catalyst or (ii) contacting the mixture of decenes with at least one C8− alpha-olefin in the presence of a second catalyst system comprising a metathesis catalyst, to provide a C16− olefin stream;
(e) hydrogenating the C16− olefin stream in the presence of a first hydrogenation catalyst to provide C16− paraffins; and
(f) using the C16− paraffins as a component to form a sustainable aviation fuel.

### Claim 2 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the mixture of decanes is blending with C16− paraffins and/or cycloparaffins to provide a sustainable aviation fuel.

### Claim 3 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the at least one C6− alpha-olefin comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, or a combination thereof.

### Claim 4 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the at least one C8− alpha-olefin comprises propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 1-hexene, 3,3-dimethyl-1-butene, 1-octene, or a combination thereof; or alternatively, propylene, 1-butene, 2-butene, 1-hexene, 1-octene, or a combination thereof.

### Claim 5 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the oligomerization product comprises 1-butene, 1-hexene, 1-octene, dodecenes, tetradecenes, or any combination thereof.

### Claim 6 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein:
(a) the sustainable aviation fuel is certified as compliant with the Carbon Offsetting and Reduction Scheme for International Aviation (CORSIA) sustainability criteria in accordance with the International Sustainability and Carbon Certification (ISCC) CORSIA certification system; or
(b) the sustainable aviation fuel is certified as a Lower Carbon Aviation Fuel (LCAF) in accordance with the International Sustainability and Carbon Certification (ISCC) LCAF certification system;
wherein the certification is based upon the weight or fraction of the sustainable aviation fuel attributable to the biomass ethanol determined by mass balance and a free attribution method.

### Claim 7 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the oligomerization product comprises:
at least 60 mol % 1-hexene, at least 60 mol % 1-octene, or at least 60 mol % 1-hexene and 1-octene combined; or
from 70 wt. % to 99.8 wt. % hexene or from 70 wt. % to 99.8 wt. % octene, and at least 0.2 wt. % of the mixture of decenes.

### Claim 8 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the mixture of decenes comprises 1-decene, 2-butyl-1-hexene, 3-propyl-1-heptene, 4-ethyl-1-octene, 5-methyl-1-nonene, 4-decene, 5-decene, or any combination thereof.

### Claim 9 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the mixture of decenes comprises from 76 mol % to 95 mol % C10 monoolefins.

### Claim 10 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the first catalyst system, the second catalyst system, or both comprise independently a chromium-based catalyst, a metallocene-based catalyst, a Ziegler-Natta based catalyst, a metal-oxide supported Group 6-10 transition metal-based catalyst, or a combination thereof.

### Claim 11 (depends on 10)

The process for making a sustainable aviation fuel according to claim 10, wherein the first catalyst system, the second catalyst system, or both further comprise a metal alkyl compound selected from an organoaluminum compound, an organoaluminoxane, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.

### Claim 12 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the first catalyst system, the second catalyst system, or both comprise independently a chromium-based catalyst, and the chromium-based catalyst comprises (a) a chromium-containing compound, (b) a heteroatomic ligand, (c) a metal alkyl compound, and (d) optionally, a diluent.

### Claim 13 (depends on 12)

The process for making a sustainable aviation fuel according to claim 12, wherein the heteroatomic ligand is selected from a pyrrole compound, a diphosphino aminyl compound, an N2-phosphinyl amidine compound, an N2-phosphinyl formamidine compound, or combinations thereof.

### Claim 14 (depends on 12)

The process for making a sustainable aviation fuel according to claim 12, wherein the heteroatomic ligand is selected from a pyrrole compound having the Formula P1 or Formula I1:
wherein: R2p, R3p, R4p, and R5p of Formula P1 and R2i, R3i, R4i, R5i, R6i, and R7i of Formula I1 is selected independently from a C1 to Cis organyl group, a C1 to C18 hydrocarbyl group, or a C3 to C60 silyl group;

### Claim 15 (depends on 12)

The process for making a sustainable aviation fuel according to claim 12, wherein the heteroatomic ligand is selected from a diphosphino aminyl moiety having Structure PNP2:
wherein the R1n, R2n, R3n, R4n, and/or R5n, independently can be: a C1 to C30 organyl group; a C1 to C30 organyl group comprising inert functional groups; a C1 to C30 hydrocarbyl group; a C1 to C30 alkyl group; a C6 to C30 aromatic group; a phenyl group or a C6 to C30 substituted phenyl group; or a substituted or an unsubstituted C1 to C20 alkyl group;
wherein any substituents are selected independently from a C1 to C10 hydrocarbyl group.

### Claim 16 (depends on 15)

The process for making a sustainable aviation fuel according to claim 15, wherein any substituent of a substituted group is selected from a halide, a C1 to C10 hydrocarbyl group, or a C1 to C10 hydrocarboxy group.

### Claim 17 (depends on 12)

The process for making a sustainable aviation fuel according to claim 12, wherein the heteroatomic ligand is selected from an N2-phosphinyl formamidine compound having Structure NPF1, or an N2-phosphinyl formamidine compound having Structure NPA1:
wherein R1, R2, R3, R4, and R5 within Structure NPF1 and Structure NPFCr1 are independently a C1 to C30 organyl group, a C1 to C30 organyl group consisting essentially of inert functional groups, or a C1 to C30 hydrocarbyl group.

### Claim 18 (depends on 12)

The process for making a sustainable aviation fuel according to claim 12, wherein the diluent comprises a hydrocarbon, a halogenated hydrocarbon, or combinations thereof.

### Claim 19 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the first catalyst system, the second catalyst system, or both comprise independently:
(a) a chromium-containing compound, a pyrrole compound, an organoaluminum compound, and optionally a halide containing compound;
(b) a chromium-containing compound, a diphosphino aminyl compound, an organoaluminum compound;
(c) a chromium-containing compound complexed to a diphosphino aminyl compound, and an organoaluminum compound;
(d) a chromium-containing compound, an N2-phosphinyl amidine compound, and an organoaluminum compound;
(e) a chromium-containing compound complexed to an N2-phosphinyl amidine compound, and an organoaluminum compound;
(f) a chromium-containing compound, an N2-phosphinyl formamidine compound, an organoaluminum compound;
(g) a chromium-containing compound complexed to an N2-phosphinyl formamidine compound, and an organoaluminum compound; or
(h) any combinations thereof.

### Claim 20 (depends on 19)

The process for making a sustainable aviation fuel according to claim 19, wherein the chromium-containing compound complexed to an N2-phosphinyl formamidine compound or the chromium-containing compound complexed to an N2-phosphinyl amidine compound have the following structures:
wherein X is an anionic ligand, and p is from 2 to 6, Q is a neutral ligand, and q is from 0 to 6; and
wherein R1, R2, R3, R4, and R5 within Structure NPF1 and Structure NPFCr1 are independently a C1 to C30 organyl group, a C1 to C30 organyl group consisting essentially of inert functional groups, or a C1 to C30 hydrocarbyl group.

### Claim 21 (depends on 19)

The process for making a sustainable aviation fuel according to claim 19, wherein the chromium-containing compound is selected from chromium(II) nitrate, chromium(II) sulfate, chromium(II) fluoride, chromium(II) chloride, chromium(II) bromide, or chromium(II) iodide, chromium(III) nitrate, chromium(III) sulfate, chromium(III) fluoride, chromium(III) chloride, chromium(III) bromide, chromium(III) iodide, a chromium(II) carboxylate, a chromium(II) alkoxide, chromium(II) aryloxide, a chromium(II) beta-dionate (i.e. beta-diketonate), a chromium(III) carboxylate, a chromium(III) alkoxide, chromium(III) aryloxide, or a chromium(III) beta-dionate (i.e. beta-diketonate).

### Claim 22 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein: wherein the first catalyst system, the second catalyst system, or both independently comprise a chromium carboxylate wherein each carboxylate group of the chromium carboxylate is independently selected from acetate, propionate, n-butyrate, isobutyrate, valerate (n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate), n-undecanoate, laurate (n-dodecanoate), or stearate (n-octadecanoate).

### Claim 23 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the first catalyst system, the second catalyst system, or both independently comprise a chromium carboxylate selected from of chromium(II) acetate, chromium(II) propionate, chromium(II) butyrate, chromium(II) isobutyrate, chromium(II) neopentanoate, chromium(II) oxalate, chromium(II) octanoate, chromium(II) 2-ethylhexanoate, chromium(II) laurate, or chromium(II) stearate, chromium(III) acetate, chromium(III) propionate, chromium(III) butyrate, chromium(III) isobutyrate, chromium(III) neopentanoate, chromium(III) oxalate, chromium(III) octanoate, chromium(III) 2-ethylhexanoate, chromium(III) 2,2,6,6,-tetramethylheptanedionate, chromium(III) naphthenate, chromium(III) laurate, or chromium(III) stearate.

### Claim 24 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the first catalyst system, the second catalyst system, or both independently comprise an organoaluminum compound selected from a triorganoaluminum compound, a diorganoaluminum halide, an organoaluminum dihalide, a diorganoaluminum alkoxide, an organoaluminum dialkoxide, an aluminoxane, or combinations thereof.

### Claim 25 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the first catalyst system, the second catalyst system, or both independently comprise:
(a) molybdenum oxide on alumina (MoO3/Al2O3), tungsten oxide on silica (WO3/SiO2), tungsten oxide on silica-alumina (WO3/SiO2/Al2O3), rhenium oxide on alumina (Re2O7/Al2O3), cobalt oxide and molybdenum oxide on alumina (CoO/MoO3/Al2O3), rhenium oxide on alumina activated with tetramethyl tin (Re2O7/Al2O3/SnMe4), or any combination thereof; or
(b) tungstated zirconium, molybdenum zirconium, nickel and/or cobalt doped tungstated zirconium, nickel and/or cobalt doped molybdenum zirconium catalysts, a Group 3 to Group 12 metal-treated zeolite, or combinations thereof.

### Claim 26 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the dehydration of the biomass ethanol comprising contacting the biomass ethanol with a dehydration catalyst under conditions suitable to form bio-ethylene, and wherein the dehydration catalyst comprises:
(a) alumina, silica gel, silica-alumina, a crystalline silicate, a dealuminated crystalline silicate, a phosphorus-modified crystalline silicate, a zeolite, a molecular sieve, or anhydrous calcium sulfate; or
(b) a lanthanum-modified H-ZSM-catalyst, a ZSM-5/SAPO-34 composite, a mordenite catalyst, microspherical SAPO-34 catalyst, a phosphorus-modified HZSM-5 catalyst, a lanthanum-phosphorous modified HZSM-5 catalyst, a gallium-modified zeolite, a gallium-modified SAPO-11, a gallium-modified HZSM-5, a ZSM-based catalyst, a heteropolyacid catalyst, or a supported heteropolyacid catalyst.

### Claim 27 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the first hydrogenation catalyst, the second hydrogenation catalyst, or both independently comprise:
(a) a heterogeneous catalyst selected from a Group 8-12 metal deposited on a carrier selected from carbon, silica, alumina, silica-alumina, a zeolite, or calcium carbonate; or
(b) a homogeneous catalysts selected from (i) a Ziegler catalysts comprising an organic salt of a Group 6-10 metal and an organoaluminum compound, or (ii) a coordination compound of Ru, Rh, or Ir, or (iii) a Group 4 metal organometallic compound.

### Claim 28 (depends on 27)

The process for making a sustainable aviation fuel according to claim 27, wherein: (a) the Group 8-12 metal of the heterogeneous catalysts is selected from Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ir, or Pt; (b) the Group 6-10 metal of the homogeneous catalyst is selected from Ni, Co, Fe, or Cr; or (c) the Group 4 metal organometallic compound is selected from a Group 4 metallocene compound.

### Claim 29 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein contacting the bio-ethylene feed with the first catalyst system occurs at a bio-ethylene feed pressure of from 0 psig (0 KPa) to 2,500 psig (17.3 MPa).

### Claim 30 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the contacting the bio-ethylene feed with the first catalyst system occurs at a temperature within a range of from 0° C. to 180° C.

### Claim 31 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the C16− olefin stream comprises:
2-ethyl-3-propyl-1-heptene, 5-propyl-1-nonene, 2-ethyl-5-methyl-1-nonene, 7-methyl-1-undecene, 2-ethyl-4-ethyl-1-octene, 6-ethyl-1-decene, 2-ethyl-1-decene, and 1-dodecene;
4-methylene-5-propylnonane, 2-methyl-5-propylnon-1-ene, 7-methyl-4-methyleneundecane, 2,7-dimethylundec-1-ene, 6-ethyl-4-methylenedecane, 6-ethyl-2-methyldec-1-ene, 4-methylenedodecane, and 2-methyldodec-1-ene;
5-methylene-6-propyl decane, 3-methylene-6-propyl decane, 5-methylene-8-methyl dodecane, 3-methylene-8-methyl dodecane, 5-methylene-7-ethyl undecane, 3-methylene-7-ethyl undecane, 2-butyl-1-decene, and 2-ethyl-1-dodecene; or
6-methylene-5-propyl dodecane, 2-butyl-5-propyl-1-nonene, 2-hexyl-5-methyl-1-nonene, 2-butyl-7-methyl-1-undecene, 6-methylene-4-ethyl tridecane, 2-butyl-6-ethyl-1-decene, 2-hexyl-1-decene, and 4-butyl-1-dodecene.

### Claim 32 (depends on 1)

The process for making a sustainable aviation fuel according to claim 1, wherein the C16− olefin stream comprises:
4-propyl-2-octene, 5-ethyl-2-nonene, 6-methyl-2-decene, 2-undecene, 2-hexene, 2-heptene, and 2-octene;
5-propyl-3-nonene, 6-ethyl-3-decene, 7-methyl-3-undecene, 3-dodecene, 3-heptene, 3-octene, and 3-nonene;
2-methyl-4-propyl-2-octene, 5-ethyl-2-methyl-2-nonene, 2,6-dimethyl-2-decene, 2-methyl-2-undecene, 2-methyl-2-hexene, 2-methyl-2-heptene, and 2-methyl-2-octene;
6-propyl-4-decene, 7-ethyl-4-undecene, 8-methyl-4-dodecene, 4-tridecene, 4-octene, 4-nonene, and 4-decene;
7-propyl-5-undecene, 8-ethyl-5-dodecene, 9-methyl-5-tridecene, 5-tetradecene, 4-nonene, 5-decene, and 5-undecene;
2,2-dimethyl-5-propyl-3-nonene, 6-ethyl-2,2-dimethyl-3-decene, 2,2,7-trimethyl-3-undecene, 2,2-dimethyl-3-dodecene, 2,2-dimethyl-3-heptene, 2,2-dimethyl-3-octene, and 2,2-dimethyl-3-nonene; or
5-propyl-6-tridecene, 5-ethyl-7-tetradecene, 11-methyl-7-pentadecene, 7-hexadecene, 4-undecene, 5-dodecene, and 6-tridecene.

### Claim 33

A process for making a sustainable aviation fuel, the process comprising:
(a) providing a bio-ethylene feed, at least a portion of which is derived from the dehydration of biomass ethanol;
(b) contacting the bio-ethylene feed with a first catalyst system comprising a first oligomerization catalyst to form an oligomerization product comprising at least one C4-C6 alpha-olefin or at least one C4-C8 alpha-olefin, and a mixture of decenes;
(c) contacting the oligomerization product with a second catalyst system comprising a second oligomerization catalyst or a metathesis catalyst to provide a C16− olefin stream;
(d) hydrogenating the C16− olefin stream in the presence of a first hydrogenation catalyst to provide C16− paraffins; and
(e) using the C16− paraffins as a component to form a sustainable aviation fuel.

### Claim 34 (depends on 33)

The process for making a sustainable aviation fuel according to claim 33, wherein the chromium-based catalyst comprises:
(a) a chromium-containing compound, a pyrrole compound, an organoaluminum compound, and optionally a halide containing compound;
(b) a chromium-containing compound, a diphosphino aminyl compound, an organoaluminum compound;
(c) a chromium-containing compound complexed to a diphosphino aminyl compound, and an organoaluminum compound;
(d) a chromium-containing compound, an N2-phosphinyl amidine compound, and an organoaluminum compound;
(e) a chromium-containing compound complexed to an N2-phosphinyl amidine compound, and an organoaluminum compound;
(f) a chromium-containing compound, an N2-phosphinyl formamidine compound, an organoaluminum compound;
(g) a chromium-containing compound complexed to an N2-phosphinyl formamidine compound, and an organoaluminum compound; or
(h) any combinations thereof.