KR-20260066141-A - Sustainable aviation fuel from normal alpha olefin byproducts and method for producing the same

Abstract

A method for producing sustainable aviation fuel (SAF) by producing a mixture of C4 - C8 alpha-olefins and byproduct C10 olefins through a specific bioethylene oligomerization reaction. This mixed decene stream is further olefinized with at least one C4 - C6 alpha-olefin to provide a C16 -olefin stream, which is upgraded by hydrogenation to become a C16 -paraffin used to form SAF. Producing a mixed decene stream that is relatively low in value due to its nonselectivity using bioethylene is to utilize such nonselectivity to an advantage for sustainable aviation fuel products where low selectivity is desirable. Such and other embodiments and aspects are described herein.

Inventors

• 웹스터-가디너 마이클 에스.
• 힐리어 제임스 엘.
• 칸칼 레자
• 펀 자레드 티.
• 비쇼프 스티븐 엠.
• 말린스키 토마스 제이.
• 지 제프리 씨.
• 컨스 스펜서 에이.

Assignees

• 셰브론 필립스 케미컬 컴퍼니 엘피

Dates

Publication Date

20260512

Application Date

20240905

Priority Date

20230907

Claims (20)

1. As a method for manufacturing sustainable aviation fuel, (a) a step of providing a bioethylene feed, wherein at least a portion thereof is derived from the dehydration of biomass ethanol; (b) a step of contacting the bioethylene feed with a first catalyst system comprising a first oligomerization catalyst to form an oligomerization product comprising a mixture of at least one C4 - C8 alpha olefin and decene; (c) a step of separating the mixture of decene from the oligomerization product; (d) (i) contacting the mixture of decene 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 decene with at least one C8 -alpha olefin in the presence of a second catalyst system comprising a double decomposition catalyst to provide a C16 -olefin stream; (e) a step of hydrogenating a C16 -olefin stream in the presence of a hydrogenation catalyst to provide C16 -paraffin; and (f) a step of forming the sustainable aviation fuel using the C16 -paraffin. A method for manufacturing sustainable aviation fuel comprising
2. As a method for manufacturing sustainable aviation fuel, (a) a step of providing a bioethylene feed, wherein at least a portion thereof is derived from the dehydration of biomass ethanol; (b) a step of contacting the bioethylene feed with a first catalyst system comprising an oligomerization catalyst to form an oligomerization product comprising a mixture of at least one C4 - C8 alpha olefin and decene; (c) a step of separating the mixture of decene from the oligomerized product; (d) a step of hydrogenating the mixture of decene in the presence of a hydrogenation catalyst to provide a mixture of decanes; and (e) forming the sustainable aviation fuel using the mixture of decanes above. A method for manufacturing sustainable aviation fuel comprising
3. A method for producing sustainable aviation fuel according to paragraph 2, wherein the mixture of decanes is blended with C16 -paraffin and/or cycloparaffin to provide the sustainable aviation fuel.
4. A method for producing sustainable aviation fuel according to claim 1, wherein at least one C6 -alpha olefin comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, or a combination thereof.
5. A method for producing sustainable aviation fuel according to claim 1, wherein 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.
6. A method for producing sustainable aviation fuel according to any one of claims 1 to 5, wherein the oligomerization product comprises 1-butene, 1-hexene, 1-octene, dodecene, tetradecene, or any combination thereof.
7. In any one of paragraphs 1 through 6, (a) The above sustainable aviation fuel is certified to comply with the sustainability standards of the International Aviation Carbon Offset and Reduction Scheme (CORSIA) in accordance with the International Sustainability and Carbon Certification (ISCC) CORSIA certification system; (b) The above sustainable aviation fuel is certified as compliant with Low Carbon Aviation Fuel (LCAF) in accordance with the International Sustainability and Carbon Certification (ISCC) LCAF certification system; A method for producing sustainable aviation fuel, wherein the above certification is based on the weight or fraction of the sustainable aviation fuel attributable to the biomass ethanol when determined through a mass balance and a free attribution method.
8. In any one of claims 1 to 6, the oligomerization product is, At least 60 mol% of 1-hexene, at least 60 mol% of 1-octene, or at least 60 mol% of 1-hexene and 1-octene; or A mixture of 70% to 99.8% by weight of hexene or 70% to 99.8% by weight of octene and at least 0.2% by weight of the decene. A method for manufacturing sustainable aviation fuel, including
9. A method for producing sustainable aviation fuel according to any one of claims 1 to 6, wherein the mixture of decene 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.
10. A method for producing sustainable aviation fuel according to any one of claims 1 to 9, wherein the mixture of decene comprises 76 mol% to 95 mol% of C 10 monoolefin.
11. A method for producing sustainable aviation fuel according to any one of claims 1 and 46, wherein the first catalyst system, the second catalyst system, or both independently comprise a chromium-based catalyst, a metallocene-based catalyst, a Ziegler-Natta-based catalyst, a Group 6 to 10 transition metal-based catalyst supported on a metal oxide support, or a combination thereof.
12. A method for producing sustainable aviation fuel according to any one of claims 1, 4 to 6 and 11, 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.
13. A method for producing sustainable aviation fuel according to any one of claims 1, 4 to 6 and 11 to 12, wherein the first catalyst system, the second catalyst system, or both independently comprise a chromium-based catalyst, and the chromium-based catalyst comprises (a) a chromium-containing compound, (b) a heteroatom ligand, (c) a metal alkyl compound, and (d) optionally, a diluent.
14. A method for producing sustainable aviation fuel according to claim 13, wherein the heteroatom ligand is selected from pyrrole compounds, diphosphinoamineyl compounds, N2 -phosphinylamidine compounds, N2 -phosphinylformamidine compounds, or combinations thereof.
15. In claim 13, the heteroatom ligand is selected from pyrrole compounds having the following formula P1 or formula I1, wherein A method for producing sustainable aviation fuel, wherein R 2p , R 3p , R 4p , and R 5p of formula P1 and R 2i , R 3i , R 4i , R 5i , R 6i , and R 7i of formula I1 are independently selected from C 1 to C 18 organic groups, C 1 to C 18 hydrocarbyl groups, or C 3 to C 60 silyl groups.
16. In claim 13, the heteroatom ligand is selected from diphosphinoamineyl moiety having the following PNP2 structure, wherein A method for producing sustainable aviation fuel, wherein R1n , R2n , R3n , R4n and/or R5n in the formula may independently be a C1 to C30 organic group; a C1 to C30 organic group comprising an inert functional group; 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 unsubstituted C1 to C20 alkyl group.
17. A method for producing sustainable aviation fuel according to claim 16, wherein any substituent of any substituted group is selected from a halide, a C1 to C10 hydrocarbyl group, or a C1 to C10 hydrocarboxyl group.
18. In claim 13, the heteroatom ligand is selected from an N2 -phosphinyl formamidine compound having the structure NPF1 or an N2 -phosphinyl formamidine compound having the structure NPA1, wherein A method for producing sustainable aviation fuel, wherein R1 , R2 , R3 , R4 , and R5 in the structure NPF1 and the structure NPFCr1 are independently C1 to C30 organic groups or C1 to C30 hydrocarbyl groups that are essentially composed of C1 to C30 organic groups or inert functional groups.
19. A method for producing sustainable aviation fuel according to claim 13, wherein the first catalyst system, the second catalyst system, or both independently comprise one or more diluents, each diluent comprising a hydrocarbon, a halogenated hydrocarbon, or a combination thereof.
20. In any one of claims 1 and 4 through 6, the first catalyst system, the second catalyst system, or both independently, (a) chromium-containing compounds, pyrrole compounds, organoaluminum compounds and optionally halide-containing compounds; (b) chromium-containing compounds, diphosphinoamineyl compounds, organoaluminum compounds; (c) A chromium-containing compound complexed with a diphosphinoamineyl compound and an organoaluminum compound; (d) chromium-containing compounds, N2 -phosphinylamidine compounds and organoaluminum compounds; (e) Chromium-containing compounds and organoaluminum compounds complexed with N2 -phosphinylamidine compounds; (f) chromium-containing compounds, N2 -phosphinylformamidine compounds, organoaluminum compounds; (g) Chromium-containing compounds and organoaluminum compounds complexed with N2 -phosphinylformamidine compounds; or (h) Any combination of these A method for manufacturing sustainable aviation fuel, including

Description

Sustainable aviation fuel from normal alpha olefin byproducts and method for producing the same Cross-reference to related applications doesn't exist. Technology sector The present disclosure relates to the production of sustainable aviation fuel (SAF) from bioethylene derived from biomass ethanol or bio-syngas ethanol. Although the jet fuel market is smaller than the gasoline and diesel fuel markets, it still accounts for approximately 25% of total transportation fuel consumption, currently exceeding 26 billion gallons annually in the United States alone. The jet fuel market is expected to roughly double over the next 20 years, while the gasoline market is projected to decline during the same period. Therefore, it is becoming increasingly important to maintain robust jet fuel production and transportation infrastructure and to develop improved methods for producing jet fuel and aviation fuel. Sustainable Aviation Fuel (SAF) can address the need to reduce emissions while providing the resilience required to meet these future needs in terms of feedstock availability. Not only can SAF significantly reduce greenhouse gas emissions with little to no changes to current engine technology, but it can also provide a drop-in fuel solution. Drop-in fuel enables current aircraft to use a 50% blend of SAF and Jet A without engine or other modifications. Additionally, SAF production facilities can be located near the airports they serve, which can also improve the issue of jet fuel transportation. Consequently, many companies are setting targets for using SAF as a key strategy to achieve net-zero emissions. However, challenges remain in the large-scale production and use of SAF. While SAF offers an environmentally sustainable technology, current SAF production technology is not yet economically feasible. For example, SAF can be four to five times more expensive than conventional jet fuel and accounts for less than 1% of the fuel currently available on the market. Therefore, there remains a need for methods to manufacture sustainable aviation fuel that can improve technology, enhance production economics, and provide additional benefits or efficiencies to address the surging demand for jet fuel. Aviation fuel primarily consists of saturated hydrocarbon compounds, including linear and branched alkanes (paraffins) and cycloalkanes (cycloparaffins or naphthenes), while aromatic compounds and olefins are present in lower concentrations. The high hydrogen-to-carbon ratio of paraffins results in high heat release per unit weight and relatively clean combustion compared to other hydrocarbons, whereas cycloparaffins have lower heat release per unit weight but increase fuel density. The composition of aviation fuel is based not on specifications based on chemical composition, but on fuel specifications that provide maximum performance for the specific aircraft in which the fuel is used. The ethylene oligomerization method described herein may be used to provide products in the kerosene jet fuel range ( C8 – C16 ) or the wide-cut jet fuel range ( C5 – C15 or C4 – C16 ). For example, JP-4 is a wide-cut fuel because it is produced over a wide distillation temperature range and contains various carbon chain lengths of 4 to 16 carbons. The approximate composition of JP-4 is about 86 volume% saturated hydrocarbons, about 13 volume% (v/v) aromatic hydrocarbons, and about 1 volume% olefin, and JP-4 has a distillation range of about 60 °C to 270 °C. A method for producing sustainable aviation fuel is based on producing bioethylene by dehydrating biomass ethanol or biosyngas ethanol, and then using a predetermined oligomerization and hydrogenation reaction to produce a product that can be used as a component of aviation fuel. In particular, the disclosed method utilizes the selective and intentional production of C4 - C8 alpha olefins from ethylene, wherein the main byproduct is a mixture of C10 olefins, also referred to herein as mixed decene. Since the mixed decene product in this normal alpha olefin (NAO) mixture is produced from an ethylene feed derived from bioethanol, the mixed decene byproduct can be further oligomerized and hydrogenated to form a sustainable aviation fuel comprising C16 -paraffins and cycloparaffins. Furthermore, the mixed decene byproduct itself can also be hydrogenated to form a decene mixture used as a component of sustainable aviation fuel by blending with C16 -paraffins and cycloparaffins, thereby providing SAF. Previously, mixed decene byproducts from ethylene oligomerization to form C4 - C8 alpha olefins were sold as undesirable products and as low-value fuel. This relatively inexpensive byproduct can be upgraded to produce aviation fuel by contacting the mixed decene with at least one C6 -alpha olefin in the presence of an oligomerization catalyst system as described herein to provide a C16 -olefin stream, and then hydrogenating it in the presence of a hydrogenation catalyst to provide sustainable aviation