FI130656B1 - A gasoline fuel component - Google Patents
A gasoline fuel component Download PDFInfo
- Publication number
- FI130656B1 FI130656B1 FI20225603A FI20225603A FI130656B1 FI 130656 B1 FI130656 B1 FI 130656B1 FI 20225603 A FI20225603 A FI 20225603A FI 20225603 A FI20225603 A FI 20225603A FI 130656 B1 FI130656 B1 FI 130656B1
- Authority
- FI
- Finland
- Prior art keywords
- paraffins
- gasoline fuel
- fuel component
- gasoline
- effluent
- Prior art date
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- 239000003502 gasoline Substances 0.000 title claims abstract description 342
- 239000000446 fuel Substances 0.000 title claims abstract description 317
- 239000000203 mixture Substances 0.000 claims description 112
- 229910052799 carbon Inorganic materials 0.000 claims description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 93
- 150000002430 hydrocarbons Chemical class 0.000 claims description 93
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 92
- 229930195733 hydrocarbon Natural products 0.000 claims description 90
- 239000004215 Carbon black (E152) Substances 0.000 claims description 58
- 239000012188 paraffin wax Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005194 fractionation Methods 0.000 claims description 18
- -1 i-pentanol Chemical compound 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 230000000035 biogenic effect Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003599 detergent Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000004227 thermal cracking Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000000543 intermediate Substances 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006078 metal deactivator Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 42
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 32
- 238000004821 distillation Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- 238000005336 cracking Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- 238000009835 boiling Methods 0.000 description 15
- 230000001965 increasing effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 13
- 238000006317 isomerization reaction Methods 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 230000001588 bifunctional effect Effects 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- 238000007872 degassing Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 description 6
- 239000008158 vegetable oil Substances 0.000 description 6
- 235000019737 Animal fat Nutrition 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001722 carbon compounds Chemical class 0.000 description 4
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical class CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 3
- 238000010606 normalization Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- WSOKFYJGNBQDPW-UHFFFAOYSA-N 4,4-dimethylheptane Chemical class CCCC(C)(C)CCC WSOKFYJGNBQDPW-UHFFFAOYSA-N 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000219198 Brassica Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 108010037444 diisopropylglutathione ester Proteins 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012487 in-house method Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
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
Herein is disclosed a gasoline fuel component comprising predominantly C4-C9 n-paraffins, C4-C9 mono-branched i-paraffins and C4-C9 multiple-branched i-paraffins. In the gasoline fuel component weight ratio of at least certain i-paraffins to certain n-paraffins is higher than in prior art gasoline components. The present gasoline fuel component may provide improved blendability, octane ratings and combustion properties.
Description
A GASOLINE FUEL COMPONENT
The present disclosure generally relates to gasoline fuels, more specifically to gasoline fuels comprising blend of gasoline components. The disclosure relates particularly, though not exclusively, to a novel gasoline fuel component obtainable from renewable feed.
This section illustrates useful background information without admission of any technigue described herein representative of the state of the art.
There is an ongoing need to reduce greenhouse gas emissions and/or carbon footprint in transportation. Accordingly, interest towards renewable transportation fuels has been growing.
Processes for producing gasoline fuel components from renewable raw materials have been proposed. However, the octane ratings for such gasoline fuel components (compared to other prior art gasoline fuel components) have been relatively low. There is a need to improve quality of renewable gasoline fuel components. Particularly, there is an interest towards producing renewable gasoline fuel components that couid be used in gasoline fuel compositions in elevated amounts together with further gasoline components.
US 2011114536 A1 discloses an aviation gasoline for aircraft piston engines and a preparation process thereof. US 2021207048 A1 discloses synthetic fuels.
It is an aim to solve or alleviate at least some of the problems related to prior art. An aim is 2 to improve the guality of gasoline fuel components obtainable from renewable sources.
O
N aN The appended claims define the scope of protection. Any examples and technical = descriptions of products, processes, and/or uses in the description and/or drawings not © 25 covered by the claims are presented not as embodiments of the invention but as examples
I
= useful for understanding the invention.
O
3 According to a first example aspect there is provided a gasoline fuel component comprising
N n-paraffins, monobranched i-paraffins, and multiple-branched i-paraffins, wherein & the sum amount of C4-C9 n-paraffins, C4-C9 mono-branched i-paraffins, and C4-C9 — muitiple-bpranched i-paraffins is more than 90 wt-% of the total gasoline fuel component weight, and wherein the weight ratio of C8 i-paraffins to C8 n-paraffin is at least 4.0, preferably at least 4.5, further preferably at least 5.0, more preferably at least 5.5, even more preferably at least 6.0, and at most 30, and the sum amount of C8 n-paraffins and C8 i-paraffins is at least 5.0 wi-%, preferably at least 5.5 wt-%, more preferably at least 6.0 wt-%, even more preferably atleast 7.0 wt-% of the total gasoline fuel component weight.
The present inventors have found the gasoline fuel component and embodiments thereof to provide advantages compared to prior art gasoline components. The advantages are related e.g to better blendability, higher octane ratings and better combustion properties discussed in more detail later.
Production of the gasoline fuel component may employ a certain process comprising a combination of hydroisomerisation and hydrocracking of a paraffinic feed. The present gasoline fuel component may be obtained from a process for producing renewable fuel components, said process further comprising recovery of an aviation fuel component.
According to a second example aspect there is provided use of the present gasoline fuel component in a gasoline fuel composition.
According to a third example aspect there is provided a gasoline fuel composition comprising the present gasoline fuel component. Said use and gasoline fuel composition provide commercial liquid transportation fuel products, where the present gasoline fuel component may contribute to the bio-content, and provide better blendability, combustion — properties and higher octane rating.
According to a fourth example aspect there is provided use of the present gasoline fuel component in feedstocks for industrial conversion processes, preferably in thermal cracking feedstocks and/or in catalytic cracking feedstocks, in solvents, in carriers, in dispersant compositions, in demulsifiers, in extractants, in detergents, in degreasing compositions, in & 25 cleaners, in thinners, in penetrating oils, in anticorrosion compositions, in multipurpose oils, a in metal working, in agriculture, in construction, in electronics, in medical appliances, in = compositions for car, electrical, textile, packaging, paper, and/or pharmaceutical industry, ? and/or in manufacture of intermediates therefor.
E Different non-binding example aspects and embodiments have been illustrated in the
E 30 foregoing. The embodiments in the foregoing are used merely to explain selected aspects
N or steps that may be utilized in different implementations. Some embodiments may be i presented only with reference to certain example aspects. It should be appreciated that corresponding embodiments may apply to other example aspects as well.
Some example embodiments will be described with reference to the accompanying figures, in which:
Fig. 1 illustrates a schematic presentation of an example embodiment of a process for producing the present gasoline fuel component.
Fig. 2 illustrates a schematic presentation of another example embodiment of a process for producing the present gasoline fuel component.
In the following description, like reference signs denote like elements or steps. — Al standards referred to herein are the latest revisions available at the filing date, unless otherwise mentioned.
Unless otherwise stated, regarding distillation characteristics, such as initial boiling points (1BP), final boiling points (FBP), T5 temperature (5 vol-% recovered), T10 temperature (10 vol-% recovered), T95 temperature (95 vol-% recovered), and boiling ranges, reference is made to EN ISO 3405-2019. IBP is the temperature at the instant the first drop of condensate falls from the lower end of the condenser tube, and FBP is the maximum thermometer reading obtained during the test, usually occurring after the evaporation of all liquid from the bottom of the flask. For boiling point distribution reference may also be made to GC-based method (simdis) ASTM D2887-19e1, or for gasoline range hydrocarbons to
ASTM D7096-19.
As used in the context of this disclosure, a "gasoline fuel component” is the subject of the present invention and formed mainly of paraffinic hydrocarbons as defined in more detail © later. it is preferably obtainable as a cut or fraction from a process or processes refining < feed material through several steps and fractionating the product(s) into cuts. Typically,
O 25 such gasoline fuel components boil, i.e. have IBF and FBP, within a range from about 25
S °C to about 210 °C, as determined according to EN ISO 3405-2019. It is meant to provide
I a component usable at least with at least one other gasoline component to form a “gasoline [an > fuel composition”. Said gasoline fuel composition refers to a product which commercially
S could be sold as gasoline, gasoline fuel, petrol, and is usable as fuel in spark-ignition
N 30 engines, said gasoline fuel compositions meeting one or more standard specifications for
N gasoline fuels, such as specifications laid down in EN 228-2012 + A1-2017. Typically, gasoline fuel compositions are blends of two or more gasoline fuel components.
As used in the context of this disclosure, aviation fuel component refers to hydrocarbon compositions suitable for use in fuel compositions meeting standard specifications for aviation fuels, such as specifications laid down in ASTM D7566-21. Typically, such aviation fuel components boil, i.e. have IBP and FBP, within a range from about 100 °C to about 300 °C, such as within a range from about 150 °C to about 300 °C, as determined according to
EN ISO 3405-2019.
As used in the context of this disclosure, diesel fuel component refers to hydrocarbon compositions suitable for use in fuel compositions meeting standard specifications for diesel fuels, such as specifications laid down in EN 15940:2016 + A1:2018 + AC:2019 or in EN 590:2022. Typically, such diesel fuel components boil, i.e. have IBP and FBP, within a range from about 160 *C to about 380 *C, as determined according to EN ISO 3405-2019.
As used herein hydrocarbons refer to compounds consisting of carbon and hydrogen.
Hydrocarbons of particular interest in the present context comprise paraffins, n-paraffins, i- paraffins, monobranched i-paraffins, multiple-branched i-paraffins, olefins, naphthenes, and aromatics. Oxygenated hydrocarbons refer herein to hydrocarbons comprising covalently bound oxygen.
As used herein paraffins refer to non-cyclic alkanes, i.e. non-cyclic, open chain saturated hydrocarbons that are linear {normal paraffins, n-paraffins) or branched (isoparaffins, i- paraffins). In other words, paraffins refer herein to n-paraffins, and/or i-paraffins.
In the context of the present disclosure, i-paraffins refer to branched open chain alkanes, i.e. non-cyclic, open chain saturated hydrocarbons having one or more alkyl side chains.
Herein, i-paraffins having one alkyl side chain or branch are referred to as monobranched i-paraffins and i-paraffins having two or more alkyl side chains or branches are herein referred to as multiple-branched i-paraffins. In other words, i-paraffins refer herein to = 25 monobranched i-paraffins and/or multiple-branched i-paraffins. The alkyl side chain(s) of i-
N paraffins may for example be C1-C6 alkyl side chain(s), preferably methyl side chain(s). > The amounts of monobranched and multiple-branched i-paraffins may be given separately.
S The term "i-paraffins” refers to sum amount of any monobranched i-paraffins and any
E multiple-branched i-paraffins, if present, indicating the total amount of any i-paraffins n 30 present regardless the number of branches. Correspondingly, “paraffins” refers to sum 3 amount of any n-paraffins, any monobranched i-paraffins, and multiple-branched i-paraffins,
N if present. &
In the context of the present disclosure, olefins refer to unsaturated, linear, branched, or cyclic hydrocarbons, excluding aromatic compounds. In other words, olefins refer to hydrocarbons having at least one unsaturated bond, excluding unsaturated bonds in aromatic rings.
As used herein, cyclic hydrocarbons refer to all hydrocarbons containing cyclic structure(s), including cyclic olefins, naphthenes, and aromatics. Naphthenes refer herein to 5 — cycloalkanes i.e. saturated hydrocarbons containing at least one cyclic structure, with or without side chains. As naphthenes are saturated compounds, they are compounds without aromatic ring structure(s) present. Aromatics refer herein to hydrocarbons containing at least one aromatic ring structure, i.e. cyclic structure having delocalized, alternating bonds all the way around said cyclic structure.
In the context of the present disclosure, for compositions boiling at <250°C (at standard atmospheric pressure), contents of n-paraffins, i-paraffins, monobranched i-paraffins, various multiple-branched i-paraffins, olefins, naphthenes, and aromatics are expressed as weight-% (wt-%) relative to the weight of the feed, stream, effluent, product, component or sample in question, or, when so defined, as weight-% (wt-%) relative to the (total) weight of paraffins, or (total) weight of i-paraffins of the feed, stream, effluent, product, component, or sample in question. Said contents may be determined by GC-FID/GC-MS method, preferably conducted as follows: GC-FID as disclosed in ASTM D6839 was run using parameters: column ZB-1 60m, ID 0.25mm, df 1.0 microns, or similar; oven 0°C (2 min) - 1.5 *C/min 300 *C (5 min); injector and detector 300 *C; carrier gas helium 1.0 ml/min; detector gases Hz 35 mi/min and air 350 ml/min; make up flow helium 30ml/min; split flow 165:1 (165 ml/min). Individual compounds were identified using GC-MS (run parameters: jon source 230°C; interface 280 °C; scan 25 - 280 m/z; scan speed 303; scan event time 0.88). Commercial tools (Shimadzu LabSolutions/GCMSSolutions and Agilent OpenLab) were used for identification of the detected compounds or hydrocarbon groups, and for determining their mass concentrations by application of response factors relative to n- & heptane to the areas of detected peaks followed by normalization to 100 wt-% (for the liquid
N volume concentrations: by application of density factors to the calculated mass = concentration of the detected peaks followed by normalization to 100 vol-%). Cyclic olefins > are lumped with naphthenes. The limit of quantitation for individual compounds of this
E 30 method is 0.1 wt-%.
S In the context of the present disclosure, for hydrocracking feeds and other compositions of
O similar boiling range, contents of n-paraffins, i-paraffins, monobranched i-paraffins, various
O multipie-branched i-paraffins, naphthenes, and aromatics, are expressed as weight % (wt- %) relative to the degassed weight of the feed stream, effluent, product, component or sample in question, or, when so defined, as weight % (wt-%) relative to the (tota!) weight of paraffins or (total) weight of i-paraffins of the feed, stream, effluent, product, component, or sample in question. Said contents may be determined by GCxGC-FID/GCxGC-MS method, preferably conducted as follows: GCxGC (2D GC) method was run as generally disclosed in UOP 990-2011 and by Nousiainen M. in the experimental section of his Master's Thesis
Comprehensive two-dimensional gas chromatography with mass spectrometric and flame jonization detectors in petroleum chemistry, University of Helsinki, August 2017, with the following modifications: The GCxGC was run in reverse mode, using a semipolar column (Rxi17Sil) first and a non-polar column (Rxi5Sil) thereafter, followed by FID detector, using run parameters: carrier gas helium 31.7 cm/sec (column flow at 40 °C 1.60 ml/min); split ratio 1:350; injector 280 °C; column T program 40 °C (0 min) - 5 *C/min - 250 °C (0 min) 10 *C/min — 300 °C (5 min), run time 52 min; modulation period 10 sec; detector 300 °C with
Hz 40 ml/min and air 400 ml/min; makeup flow helium 30 ml/min; sampling rate 250 Hz and injection size 0.2 microliters. Individual compounds were identified using GCxGC-MS, with
MS-parameters: ion source 230 °C; interface 300 °C; scan range 25 - 500 amu; event time — (sec) 0.05; scan speed 20000. Commercial tools (Shimadzu's LabSolutions, Zoex's GC
Image) were used for data processing including identification of the detected compounds or hydrocarbon groups, and for determining their mass concentrations by application of response factors relative to n-heptane to the volumes of detected peaks followed by normalization to 100 wt-%. Olefins were lumped with naphthenes and heteroatomic species with aromatics, unless separately reported. The limit of quantitation for individual compounds of this method is 0.1 wt-%.
In the context of the present disclosure, various characteristics of the feeds, streams, effiuents, products, components, or samples are determined according to the standard methods referred to or disclosed herein, as properly prepared. For example, cloud point is determined according to ASTM D 5771-17 from a degassed feed, stream, effluent, product, co component, or sample.
N As used herein, hydroisomerisation (HI) effluent refers to total HI effluent, degassed Hi = effluent, or degassed and stabilised HI effluent, as the case may be.
O
? In the context of this disclosure, CX+ paraffins, CX+ n-paraffins, CX+ i-paraffins, CX+ mono- o 30 branched i-paraffins, CX+ multiple-branched i-paraffins, CX+ hydrocarbons, or CX+ fatty
S acids refer to paraffins, n-paraffins, i-paraffins, mono-branched i-paraffins, multiple-
N branched i-paraffins, hydrocarbons, or fatty acids, respectively, having a carbon number of < at least X, where X is any feasible integer. It is understood that every compound falling within the definition is not necessarily present.
in the context of this disclosure, CY- paraffins, CY- n-paraffins, CY- i-paraffins, CY- mono- branched i-paraffins, CY- multiple-branched i-paraffins, CY- hydrocarbons, or CY- fatty acids refer to paraffins, n-paraffins, i-paraffins, mono-branched i-paraffins, multiple- branched i-paraffins, hydrocarbons, or fatty acids, respectively, having a carbon number of atmostY, wherein Y is any feasible integer. In the context of this disclosure, CXy-CXz (or
CXy to CXz) paraffins, CXy-CXz n-paraffins, CXy-CXz i-paraffins, CXy-CXz mono-branched i-paraffins, CXy-CXz multiple-branched i-paraffins, CXy-CXz hydrocarbons, or CXy-CXz fatty acids refer to a range of paraffins, n-paraffins, i-paraffins, mono-branched i-paraffins, multipie-branched i-paraffins, hydrocarbons, or fatty acids respectively, where Xy and Xz are feasible end-value integers, wherein the carbon numbers within such range is as indicated by the end-value integers and any integers between said end-values, if present.
However, paraffins, n-paraffins, i-paraffins, mono-branched i-paraffins, multiple-branched i- paraffins, hydrocarbons, or fatty acids, as the case may be, of all said carbon numbers within said range, particularly at or around the end points, may not necessarily be present — (except when so expressly indicated). On the other hand, isomers, by definition, may comprise several compounds having the same carbon number, such as C9 isomers, may comprise methyl octanes (different positions of the methyl-branch), dimethyl heptanes (different positions of the two methyi-branches), etc, wherein “C9 isomers” comprises the sum amount of all such variants. Typically, a sum amount as of weight or volume of paraffins, n-paraffins, i-paraffins, mono-branched i-paraffins, multiple-branched i-paraffins, hydrocarbons, or fatty acids, as defined each time, of all carbon numbers included is meant.
For example, C4-C9 n-paraffins refers to any n-paraffins within said range, such as C4, C5,
Cg, C7, C8, and C9 n-paraffins, even if the content of C9 n-paraffins was zero. In other words, a sum amount is obtainable by addition of O (referring to absent C9 n-paraffins) to — the sum weight of all other C4 to C9 n-paraffins present.
O Isomerisation converts at least a certain amount of n-paraffins to i-paraffins, especially to
S mono-branched i-paraffins. By (further) raising the isomerization degree, for example by
O increasing severity of the hydroisomerisation as described hereinafter, more n-paraffins can
S be converted to i-paraffins, and mono-branched i-paraffins can be converted to multiple-
I 30 branched i-paraffins, such as di-branched, tri-branched i-paraffins, even i-paraffins - comprising more than three branches.
O
3 Ås used herein and in the context of the second reactor section, degree of effective cracking
N refers to cracking that yields non-gaseous (NTP) cracking products, especially as
N expressed as the ratio of the C8 to C14 hydrocarbon content in the hydrocracking effluent tothe C8 to C14 hydrocarbon content in the second reactor section feed.
As used herein, the term renewable refers to compounds or compositions that are obtainable, derivable, or originating from plants and/or animals, including compounds or compositions obtainable, derivable, or originating from fungi and/or algae, in full or in part.
As used herein, renewable compounds or compositions may comprise gene manipulated compounds or compositions. Renewable feeds, components, compounds, or compositions may also be referred to as biological feeds, components, compounds, or compositions, or as biogenic feeds, components, compounds, or compositions.
As used herein, the term fossil refers to compounds or compositions that are obtainable, derivable, or originating from naturally occurring non-renewable compositions, such as crude oil, petroleum oil/gas, shale oi/gas, natural gas, or coal deposits, and the like, and combinations thereof, including any hydrocarbon-rich deposits that can be utilized from ground/underground sources. The term circular refers to recycled material typically originating from non-renewable sources. For example, the term circular may refer to recycled material originating from waste plastics. — Said renewable, circular, and fossil compounds or compositions are considered differing from one another based on their origin and impact on environmental issues. Therefore, they may be treated differently under legislation and regulatory framework. Typically, renewable, circular, and fossil compounds or compositions are differentiated based on their origin and information thereof provided by the producer.
Chemically the renewable or fossil origin of any organic compounds, including hydrocarbons, can be determined by suitable method for analyzing the content of carbon from renewable sources e.g. DIN 51637 (2014), ASTM D6866 (2020), or EN 16640 (2017).
Said methods are based on the fact that carbon atoms of renewable or biological origin comprise a higher number of unstable radiocarbon (**C) atoms compared to carbon atoms n 25 of fossil origin. Therefore, it is possible to distinguish between carbon compounds derived
S from renewable or biological sources or raw material and carbon compounds derived from
S non-renewable or fossil sources or raw material by analyzing the ratio of ”C and "C 2 isotopes. Thus, a particular ratio of said isotopes can be used as a “tag” to identify a ? renewable carbon compound and differentiate it from non-renewable carbon compounds. s 30 The isotope ratio does not change in the course of chemical reactions. Therefore, the
S isotope ratio can be used for identifying renewable compounds, components, and
O compositions and distinguishing them from non-renewable, fossil materials in reactor feeds,
O reactor effluents, separated product fractions and various blends thereof. Numerically, the biogenic carbon content can be expressed as the amount of biogenic carbon in the material as a weight percent of the total carbon (TC) in the material (in accordance with ASTM D6866
(2020) or EN 16640 (2017)). In the present context, the term renewable preferably refers to a material having a biogenic carbon content of more than 50 wi-%, especially more than 60 wi-% or more than 70 wi-%, preferably more than 80 wt-%, more preferably more than 90 wi-% or more than 95 wt-%, even more preferably about 100 wt-%, based on the total weight of carbon in the material (EN 16640 (2017)).
According to a first aspect, herein is provided a gasoline fuel component comprising n- paraffins, monobranched i-paraffins, and muttiple-bpranched i-paraffins, wherein the sum amount of C4-C9 n-paraffins, C4-C9 mono-branched i-paraffins and C4-C9 multiple- branched i-paraffins is more than 90 wt-% of the total gasoline fuel component weight, and wherein the weight ratio of C8 i-paraffins to C8 n-paraffins is at least 4.0, and at most 30, and the sum amount of C8 n-paraffins and C8 i-paraffins is at least 5.0 wt-%.
The gasoline fuel component is highly paraffinic, mainly comprising n-paraffins, monobranched i-paraffins, and multiple-pranched i-paraffins. The carbon number distribution may be relatively broad, but is typically limited by the boiling points of hydrocarbons therein, as the gasoline fuel component is preferably recovered as a distillation fraction. In any case, the carbon number distribution of the paraffins in the gasoline fuel component covers typically at least three adjacent carbon numbers, preferably at least four adjacent carbon numbers, more preferably at least five adjacent carbon numbers, within the C4-C9 range.
The gasoline fuel component is characterized by the sum amount of C4-C9 n-paraffins, C4-
C9 mono-branched i-paraffins, and C4-C9 multiple-branched i-paraffins, which in total is more than 90 wt-% of the total gasoline fuel component weight. However, it should be noted that said sum amount is defined adding together the amounts of any paraffins having relevant carbon numbers (i.e. falling within said carbon number range, including end points) e 25 found in analysis. On the other hand, it should not be understood as indicating presence of
S paraffins having all carbon numbers falling within said range. 2 C8 paraffins are usable in gasoline fuels and may be present in varying amounts in highly
S paraffinic gasoline components, depending inter alia on the distillation end points used in = the recovery of the gasoline fractions. However, the RON of n-C8 is as low as -20 so its - 30 presence can be detrimental to the octane rating of the gasoline fuel component. Eliminating 3 all C8 paraffins from the recovered gasoline fuel component e.g. by reducing the FBP of the
N gasoline fuel component would cause unacceptable yield reduction of said component.
N Surprisingly, it was found that by controlling the weight ratio of C8 i-paraffins to C8 n- paraffins to be at least 4.0, preferably at least 4.5, further preferably at least 5.0, more preferably at least 5.5, even more preferably at least 6.0, typically at most 30, or at most 25, or at most 20, it is possible to obtain components with good octane ratings without a need to eliminate C8 paraffin content. To the contrary, C8 paraffins may be incorporated in substantial amounts, preferably at least 5.0 wt-%, further preferably at least 5.5 wt-%, more preferably at least 6.0 wi-%, or even more preferably at least 7.0 wt-%, typically up to 50 wt-%, or up to 40 wt-%, or up to 30 wt-%, or up to 25 wt-%, such as from 4.0 to 50 wt-%, or from 4.5 to 50 wt-%, or from 5.0 to 40 wt-% of the total gasoline fuel component weight without destroying the component's octane rating, provided the ratio of C8 i-paraffins to C8 n-paraffins as defined above is met. Actually, even significant improvement may be seen — compared to conventional paraffinic gasoline components.
In general, C7 paraffins are abundant in highly paraffinic gasoline components due to distillation processes for recovery of gasoline fractions. Characterizing embodiments of the present gasoline fuel component by its C7 paraffins content highlights interesting qualities.
In certain embodiments, in total, the amount of C7 paraffins of the total gasoline fuel component weight is at least 15 wt-%, preferably at least 20 wt-%, such as within a range from 15 wt-% to 40 wt-%, or from 15 wt-% to 35 wt-%, or from 15 wt-% to 30 wt-%. C7 paraffins refers to the sum amount of C7 n-paraffins, C7 mono-branched i-paraffins, and C7 multiple-branched i-paraffins. Nevertheless, the octane rating for n-heptane, the C7 n- paraffin, is O, which lowers the RON and MON values of the gasoline fuel component and eventual gasoline fuel composition.
Therefore, it is beneficial to have as high i-C7/n-C7 ratio as feasible, to improve the RON of the gasoline fuel component. In certain embodiments, the weight ratio of C7 i-paraffins to
C7 n-paraffins (i-C7/n-C7 ratio) is at least 2.7, preferably at least 2.8, preferably at least 2.9, preferably at least 3.0, preferably at least 3.1, preferably at least 3.2, preferably at least 3.4.
If has been found that in highly paraffinic compositions such i-C7/n-C7 ratios may be an & indication of a particularly high-quality gasoline component, as shown by the Examples. In
N practice, an upper limit for said ratio stems from reasonable isomerisation degree, so that = said ratio may be at most 5.0 or at most 10. Hence, said ratio may vary from 2.7 to 10, such > as from 3.4 to 5.0. Conventional paraffinic gasoline fuel components, such as those derived
E 30 from hydrodeoxygenation of vegetable oils, tend to have lower i-paraffin contents, especially 0 for lower carbon numbers, such as C7.
O Yet another single carbon number of interest is C6, and here again, it is beneficial to keep
O the C6 n-paraffin, the n-hexane, content low, to improve the RON, and also due to its suspected properties of concern to health and/or environment. Accordingly, in certain embodiments, the C6 n-paraffin content of the gasoline fuel component is at most 11 wt-%,
at most 9 wt-%, at most 8 wt-% of the tota! gasoline fuel component weight, such as from 0.5 wt-% to 11 wt-% or from 0.5 wt-% to 8 wt-% of the tota! gasoline fuel component weight.
The total amount of C6 paraffins in the gasoline fuel component is typically at least 10 wt- %, and at most 40 wt-% of the total gasoline fuel component weight. With higher total C6 — paraffin contents also the absolute C6 n-paraffin contents tend to be higher, but in any case, in the present gasoline fuel components the weight ratio of C6 i-paraffins to C6 n-paraffin is preferably more than 1.0.
Even though C6 represents a typical carbon number for any hydrocarbon-based gasoline, the present gasoline component may be specifically advantageous because of relatively — high i-paraffin content, which may apply to C6 paraffins as well. In such embodiments, even though the C6 paraffins were abundant, the n-hexane content is not worryingly high because of highly i-paraffinic composition. The relatively high i-paraffin content in relation to the n-paraffin content for carbon number 6 paraffins may be given as the weight ratio of
C6 i-paraffins to C6 n-paraffins. Therefore, in certain embodiments, the present gasoline fuel component can be characterized by the weight ratio of C6 i-paraffins to C6 n-paraffins being at least 1.5, preferably at least 1.7 and more preferably at least 2.0.
Typical embodiments of the present gasoline fuel component may comprise at least C6, C7 and C8 paraffins. Considering the i-paraffin content in relation to the n-paraffin content for carbon numbers 6-8, these embodiments can be characterized by the weight ratio of C6-
C8 i-paraffins to C6-C8 n-paraffins being at least 2.7, preferably at least 2.8 and more preferably at least 30. As seen in the Examples, C6, C7 and C8 may in certain embodiments be the most abundant carbon numbers of the gasoline fuel component.
Hence, the weight ratio of C6-C8 i-paraffins to C6-C8 n-paraffins gives a very good representation of such embodiments of the present gasoline fuel component. Having such ahighisomerization degree within this carbon number range C6-C8, is by no means typical & for prior art gasoline cuts. Furthermore, as RON of n-C6 paraffin is 25, of n-C7 paraffin O
N and of n-C8 paraffin -20, their presence may be detrimental to octane rating of the gasoline = fuel component. Eliminating all C8 paraffins let alone all C7 and C8, and even C6 paraffins, > e.g. by reducing FBP of the component, would cause unacceptable vield reduction of the
E 30 component. Surprisingly, it was found that by controlling the weight ratio of C6-C8 i-paraffins 0 to C6-C8 n-paraffins as specified provides components with good octane ratings without a © need to eliminate or even minimize content of C7 and C8 paraffins. To the contrary, C6-C8
N paraffins may be incorporated in elevated amounts without destroying gasoline fuel
N component's octane rating. Preferably, the sum amount of C6-C8 n-paraffins and C6-C8 i- paraffins is at least 50 wt-%, more preferably at least 55 wt-%, even more preferably at least
58 wt-% of the total gasoline fuel component weight, typically up to 95 wt-%, or at most 90 wt-%, or at most 85 wt-% of the total gasoline fuel component weight. Such sum amounts of C6-C8 n-paraffins and C6-C8 i-paraffins in the gasoline fuel component may provide significant improvement over conventional paraffinic gasoline components.
Another feature correlating with desired characteristics of the gasoline fuel component is the weight ratio of the sum amount of C6-C9 multiple-branched i-paraffins to the sum amount of C6-C9 n-paraffins. According to certain preferred embodiments, said weight ratio of C6-C9 multiple-branched i-paraffins to C6-C9 n-paraffins is at least 0.2, preferably at least 0.3, more preferably at least 0.4, even more preferably at least 0.5. Said ratio may be upto 1.5 or even up to 2.0. An elevated weight ratio of C6-C9 multiple-branched i-paraffins to C6-C9 n-paraffins improves the RON of the highly paraffinic gasoline fuel component significantly. Compared to monobranched i-paraffins, multiple-branched i-paraffins are more effective in compensating low RON of n-paraffins. Conventional gasoline components derived from hydrodeoxygenation of vegetable oils have lower multiple-branched i-paraffin contents. While the octane number for n-heptane is zero, both RON and MON for n-C8 and n-C9, namely n-octane and n-nonane, are even lower, below zero.
Gasoline fuel component that is highly isomerised has been found to provide benefits related to octane ratings over n-paraffinic compositions. Hence, according to certain preferred embodiments, the gasoline fuel component comprises at least 50 wt-%, preferably atleast 55 wt-%, more preferably at least 60 wt-%, even more preferably at least 65 wt-%
C4-C9 i-paraffins of the total gasoline fuel component weight, and/or at least 5 wt-%, preferably at least 6 wi-%, more preferably at least 7 wt-%, even more preferably at least 10 wt-%, or at least 11 wt-% C6-C9 multiple-branched i-paraffins of the total gasoline fuel component weight. Hence, in such embodiments, the gasoline fuel component is predominantly i-paraffinic, and a notable part of said i-paraffins may contain more than one & branch. Gasoline fuel components having such contents of C4-C9 i-paraffins and/or C6-C9
N multiple-branched i-paraffins significantly improve the RON of the (highly paraffinic) = gasoline fuel component, compared to conventiona! gasoline components derived from > hydrodeoxygenation of vegetable oiis that may have elevated i-paraffin contents, but lower
E 30 — multiple-branched i-paraffin contents, especially for said lower carbon numbers. 2 The research octane number and the motor octane number, RON and MON respectively,
LO may be measured for the neat gasoline component or for the gasoline component blended
O with another gasoline component having a known octane number, then given as bRON and
PMON, respectively. Acronyms RON, bRON, MON and bMON as used throughout this text refer to measured RON, bRON, MON and bMON after correction, i.e. they are the corrected values obtained after subtracting 0.2 from the measured values (in accordance with section 5.6 of EN228:2012 amended 2017). Throughout this text clean research and motor octane numbers are meant, i.e. as achieved without using octane number boosting additives. A standard method for RON and MON measurements is given e.g. in ASTM D2699/D2700.
Measuring and calculating bRON is known in the field and has been published for example in US4244704A. In the experimental part of the present disclosure, gasoline fuel component according to the present disclosure was studied in blends with a typical gasoline component. Surprisingly, the bRON and bMON results for the gasoline fuel component according to the present disclosure were significantly better than for another renewable paraffinic gasoline component used as a reference in said experiments. The poor octane ratings of the reference gasoline component set a limitation for its use in blends, because too high amount thereof in a gasoline composition would cause the octane ratings falling short of target. Therefore, compared to said reference renewable gasoline component, a larger share of the present gasoline fuel component may be incorporated into gasoline fuel composition without compromising the target octane. Hence, according to certain embodiments, the gasoline fuel component has a bRON of at least 51, preferably at least 55. According to certain embodiments, the gasoline fuel component has a bMON of at least 48, preferably at least 50, even at least 55.
The present inventors have also found that the present gasoline fuel component comprising high content of paraffins within carbon number range C4-C9 may be highly beneficial in comparison to prior art gasoline components for several reasons. For example, the highly paraffinic gasoline fuel components of the present disclosure have naturally low total content of other compounds than paraffins. For example, total content of aromatics, olefins and naphthenes is typically less than 5.0 wt-%, such as less than 4.0 wt-%, often at most 3.0 wt-%, of the total gasoline fuel component weight. Among these, total content of
O aromatics is typically less than 3.0 wi-%, often less than 2.0 wt-% of the total gasoline fuel
S component weight. The low aromatics content contributes e.g. to reducing deposit formation
O in engines and injectors. All in all, incorporation of the highly paraffinic gasoline fuel
S component in blends supports meeting standards, such as EN 228, particularly considering
I 30 limits for aromatics and benzene. High paraffins content may also provide ready > biodegradability. Further, the highly paraffinic gasoline fuel components may provide better
S performance regarding burning and/or emissions to the end user. Further, the blendability
N of the present gasoline fuel component to other typical gasoline components is very good. x Further, the highly paraffinic gasoline fuel component is more stable or more inert e.g. — during storage and in blends, compared to components with higher content of non-paraffinic compounds, particularly of olefins, that might react and form high molecular weight precipitates, i.e. gums, in the component or in gasoline fuel composition thereof. Typically, the total content of olefins is less than 1000 vol-ppm of the total gasoline fuel component weight. Also, aromatics can be susceptible to instability, particularly with increasing aromatic size and concentration, resulting in a higher deposition propensity upon stressing e.g. caused by oxidation and molecular growth of the aromatics. Improved stability is particularly desired property e.g. for hybrid vehicles using another primary power source, such as electricity or gas, and gasoline only as a secondary fuel which is retained in the fuel system for longer periods. Additionally, a range of paraffins, such as a range within C4-C9, is more beneficial for the end product properties when blended to other typical gasoline components than a neat or pure component, such as neat n-heptane.
Hence, according to certain preferred embodiments, in the present gasoline fuel component the sum amount of C4-C9 n-paraffins, C4-C9 mono-branched i-paraffins, and C4-C9 multipie-branched i-paraffins is more than 93 wt-%, preferably more than 95 wt-%, more preferably from 95 to 99 wt-% of the tota! gasoline fuel component weight.
When the content of paraffins within carbon number range C4-C9 is high, the total amount of any hydrocarbons with 3 carbon atoms or less (C3- hydrocarbons), namely C1-C3 hydrocarbons, is low, typically at most 4.0 wt-%, or at most 3.5 wt-%, or at most 3.0 wt-% of the total gasoline fuel component weight. Limiting the presence of light hydrocarbons, namely hydrocarbons with 3 carbon atoms or less, improves handling of the component and any products, such as gasoline fuel compositions, thereof.
By studying the paraffins within carbon number range C4-C9 of the present gasoline fuel component further, the present inventors also defined average carbon numbers for n- paraffins and i-paraffins within said carbon number range. According to certain embodiments of the gasoline fuel component, the average carbon number of C4-C9 n- n 25 paraffins is ai most 6.0, preferably at most 5.6. Preferably, the average carbon number falls
S between 5.0 and 6.0 or within a range from 5.0 to 6.0. Compared to the average carbon oO number of the C4-C9 i-paraffins in the gasoline fuel component, the C4-C9 n-paraffins have = an average carbon number which is at least 0.5 units lower, preferably at least 0.6 units ? lower than the average carbon number of corresponding C4-C9 i-paraffins. This was found s 30 to contribute to octane numbers so that the lower the average carbon number of C4-C9 n-
S paraffins, the higher the RON of the gasoline fuel component. The average carbon number
O for i-paraffins was found to be higher and thus, according to certain embodiments, the
O average carbon number of C4-C9 i-paraffins is more than 6.0, preferably at least 6.2, more preferably within the range from 6.2 to 8.0. RON of n-paraffins tend to increase along decreasing carbon number. For example, n-C8 and n-C9 have RON -20 or less, n-C7 has
RON of O, n-C6 has RON of 25, n-C5 has RON of 82 and n-C4 has RON of 94. Additionally,
RON of paraffins tend to increase along increasing degree of branching, mono-branched i- paraffins having somewhat higher and muitiple-branched i-paraffins significantly higher octane numbers compared to n-paraffins of the same carbon number. Reducing the average carbon number of C4-C9 range paraffins in the component e.g. by reducing component's FBP, would cause unacceptable yield reduction. Also, increasing the degree of branching up to the hilt would be uneconomical, and also unnecessary. Surprisingly it was found that by controlling the average carbon number of C4-C9 n-paraffins and/or C4-
C9 i-paraffins as specified above, it is possible to provide gasoline fuel components with good octane ratings without a need to reduce the FBP excessively or to increase the degree of branching up to the hilt.
The present gasoline fuel component is obtainable by a process, defined in detail later, from a renewable feedstock providing a high bio-content for the products thereof. The biogenic carbon content may be defined for any feasible composition according to EN 16640 (2017).
According to certain embodiments, the biogenic carbon content of the gasoline fuel component is at least 50 wt-%, preferably at least 70 wt-%, more preferably at least 90 wt- %, or at least 95 wt-%, or even about 100 wt-%, based on the total weight of carbon (TC) in the gasoline fuel component. The present gasoline fuel component contributes to the bio- content of the total gasoline fuel composition, advantageously increasing its bio-content.
The present gasoline fuel component may be obtained as a fraction recovered from a process developed for production of high-quality liquid transportation fuel components, specifically optimised for yielding renewable and/or sustainable aviation fuels, as illustrated by the Examples. In certain preferred embodiments, an aviation fuel component is recovered in addition to said gasoline fuel component from the fractionation, both usable as liquid transportation fuel components. The combined recovery of the gasoline fuel & component and the aviation fuel component provides efficient use of the feed to the process
N and higher value products from refining. Generally, gasoline fuel and aviation fuel may have = relatively small overlap with regard to boiling points and hydrocarbon distribution. Hence, > the present gasoline fuel component and a (renewable) aviation fuel component, may be
E 30 recovered from fractionation, e.g by distillation, as subsequent cuts. Additionally, process
O choices improving the aviation fuel component guality, e.g. hydrocracking an isomerized : paraffin stream, improve the gasoline fuel component quality as well, particularly
N blendability, octane ratings, and combustion properties.
N
The present gasoline fuel component's beneficial characteristics, especially the elevated i- — paraffin/n-paraffin ratio in lower carbon number paraffins, may be contributed by the production process and a feed thereto. The gasoline fuel component may be directly obtainable or obtained from product recovery of the production process.
Hence, according to certain embodiments, the present gasoline fuel component is obtainable or obtained by a process comprising providing a paraffinic hydrocarbon feed comprising at least 60 wt-% paraffins of the total weight of the paraffinic hydrocarbon feed, of which paraffins at most 30 wt-% are i- paraffins; subjecting the paraffinic hydrocarbon feed in a first reaction section, preferably in a first reactor, to hydroisomerisation in the presence of a hydroisomerisation catalyst to obtain a hydroisomerisation effluent; subjecting a second reaction section feed comprising at least a portion of the hydroisomerisation effluent to hydrocracking in a second reaction section, preferably in a second reactor, in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent; subjecting the hydrocracking effluent, and optionally (at least) a portion of the hydroisomerisation effluent, to fractionation, and recovering from the fractionation at least a gasoline fuel component, and optionally an aviation fuel component.
Optionally, also other products, such as a diesel fuel component, may be recovered.
Preferably, the process further comprises recovering from the fractionation a recycle — stream, preferably having a T5 temperature (5 vol-% recovered, EN ISO 3405-2019) of 270 °C or higher, and optionally comprising C18 n-paraffins. The recycle stream may be comprised in the at least a portion of the hydroisomerisation effluent, or form the at leasta portion of the hydroisomerisation effluent subjected to hydrocracking in the second reaction section, preferably second reactor. in other words, the recycle stream is subjected, as part n 25 of the second reaction section feed, to hydrocracking in the second reaction section,
S preferably in the second reactor. The recycle stream may comprise at least a portion of the oO fractionation bottom. In embodiments where a recycle stream is separated, the yield of o desired liquid fuel component(s) can be further optimised, particularly in embodiments
I where the second reaction section feed fed to hydrocracking comprises in addition to the s 30 recycle stream a further portion of the hydroisomerisation effluent. In embodiments where
S a recycle stream is separated, a diesel fuel component may be conveniently recovered by
N separating a portion from the recycle stream. & In the present process, the paraffinic hydrocarbon feed comprises at least 60 wt-%, preferably at least 70 wt-%, more preferably at least 80 wt-%, even more preferably at least
90 wt-% paraffins of the tota! weight of the paraffinic hydrocarbon feed. The paraffinic hydrocarbon feed of the present disclosure may comprise even at least 95 wt-% paraffins of the total weight of the paraffinic hydrocarbon feed or consist essentially of paraffins. The paraffinic hydrocarbon feed of the present disclosure may contain minor amounts of olefins, preferably less than 5 wi-%, more preferably less than 1 wt-%, based on the total weight of the paraffinic hydrocarbon feed, as well as minor amounts of aromatics and/or naphthenes.
An advantage of using a highly paraffinic hydrocarbon feed in the process of the present disclosure is that paraffins are isomerised relatively easily and at milder conditions when subjected to hydroisomerisation compared to e.g. cyclic hydrocarbons. Also, paraffins crack relatively easily and at milder conditions when subjected to hydrocracking, which helps to reduce formation of light gases.
In the present process, the paraffinic hydrocarbon feed comprising at least 60 wt-% paraffins of the total weight of the paraffinic hydrocarbon feed, of which paraffins at most 30 wi-% are i-paraffins, may be obtained from a paraffinic hydrotreatment effluent, such as a — hydrodeoxygenation (HDO) effluent, a paraffinic Fischer-Tropsch (FT) effluent, or a combination thereof, after having subjected said effluent(s) at least to gas-liquid separation, i.e. removal of at least compounds that are gaseous at NTP, and optionally also to paraffinic feed fractionation(s). While e.g. paraffinic FT effluents of fossil origin are readily available (in addition to FT effluents of renewable origin), preferably the paraffinic hydrocarbon feed ofthe present disclosure is at least partially renewable, i.e. comprises biogenic components.
Preferably, the paraffinic hydrocarbon feed of the present disclosure comprises or consists essentially of a hydrodeoxygenation (HDO) effluent, or a fraction thereof, such as a degassed hydrodeoxygenation effluent or a fraction thereof, from catalylic hydrodeoxygenation (catalytic HDO) of an oxygenated hydrocarbon feed. Preferably the n 25 oxygenated hydrocarbon feed comprises at least one or more of vegetable oil, animal fat
S and/or microbial oil. This kind of paraffinic hydrocarbon feeds tend to have relatively narrow oO carbon number distribution and therefor benefit more from being subjected to the present o process, compared eg to FT-based feeds usually having substantially Gaussian
I distribution of hydrocarbon chains and a wide carbon chain length distribution. Typically s 30 providing the paraffinic hydrocarbon feed comprises subjecting an oxygenated hydrocarbon
S feed to hydrodeoxygenation in the presence of a hydrodeoxygenation catalyst to obtain a
N hydrodeoxygenation effluent, and then subjecting the hydrodeoxygenation effluent to gas- < liquid separation, and optional paraffinic feed fractionation to obtain as the paraffinic hydrocarbon feed the degassed hydrodeoxygenation effluent or a fraction thereof
Hydrodeoxygenation may be conducted as described in prior art publications, such as
F1100248B, EP1741768A1, EP2155838B1 or F1129220 B1.
Generally, in the context of the present disclosure, hydroisomerisation (HI) of the paraffinic hydrocarbon feed in the first reaction section/reactor is operated so that isomerisation reactions prevail while cracking reactions are controlied or suppressed. Typically the Hi in the first reaction section/reactor is conducted at a temperature within a range from 200 °C to 500 °C, preferably from 230 °C to 500 °C, more preferably from 250 °C to 450 °C, even more preferably from 280 °C to 400 °C, a pressure within a range from 1 MPa to 10 MPa, preferably from 2 MPa to 8 MPa or from 3 MPa to 10 MPa, a Ha partial pressure at the inlet — of the first reaction section/reactor within a range from 1 MPa to 10 MPa, preferably from 2
MPa to 8 MPa, a weight hourly space velocity within a range from 0.1 to 10, preferably from 0.2 to 8, more preferably from 0.4 to 6 kg paraffinic hydrocarbon feed per kg catalyst per hour, and a Ha to paraffinic hydrocarbon feed ratio within a range from 10 to 2000, preferably from 50 to 1000 normal liters Ha per liter paraffinic hydrocarbon feed. Hydroisomerisation may be conducted as described in prior art publications, such as FI1100248B,
EP1741768A1, EP2155838B1 or FI129220 B1. Severity of the HI may be increased by at least one or more of decreasing VVHSV, increasing temperature, and/or increasing pressure. When using fresh Hi catalyst, high severity Hi conditions may be reached at lower temperature and/or pressure, and/or using higher WHSV, and towards the end of the Hi catalyst lifetime higher temperature and/or pressure, and/or lower WHSV may be needed to reach even medium severity HI. In the present context, HI that yields liquid effluents having, as wt-% of paraffins in the liquid effluent, total i-paraffins content 50-85 wt-% and multipie-branched i-paraffins content at most 25 wt-%, or total i-paraffins content 85-95 wt- % and multiple-branched i-paraffins content 25-55 wt-%, or total i-paraffins content at least 95wt-% and multiple-branched i-paraffins content more than 55 wt-%, is generally regarded
O as HI of low severity or medium severity or high severity, respectively, although these
S content ranges are merely for illustrating the order of magnitude, and may overlap to some
O extent, and vary from case to case. > Generally, hydrocracking in the second reaction section/reactor is operated so that cracking
E 30 reactions, especially those enhancing degree of effective cracking, particularly to C8-C14
O hydrocarbons but also to lighter non-gaseous hydrocarbons, are more abundant than in the 3 hydroisomerisation in the first reaction section/reactor. Preferably cracking reactions,
N especially those enhancing the degree of effective cracking, prevail in the hydrocracking in
N the second reaction section/reactor, yet generally without excessive cracking and excessive fuel gas formation. Typically the hydrocracking in the second reaction section/reactor is conducted at a temperature within a range from 200 °C to 450 °C, preferably from 220 °C to 430 °C, more preferably from 280 °C to 350 °C, a pressure within a range from 0.4 MPa to 8 MPa, preferably from 1 MPa to 7 MPa, a Ha partial pressure at the inlet of the second reaction section/reactor within a range from 0.4 MPa to 8 MPa, preferably from 1 MPa to 7
MPa, a weight hourly space velocity within a range from 0.1 to 10, preferably from 0.2 to 8, more preferably from 0.4 to 8, even more preferably from 0.5 to 1.5 kg second reactor feed per kg catalyst per hour, and a Ha to second reactor feed ratio within a range from 10 to 2000, preferably from 50 to 1000 normal liters Ha per liter second reactor feed.
Preferably, the hydroisomerisation catalyst is a non-sulphided bifunctional — hydroisomerisation catalyst and the hydrocracking catalyst is a non-sulphided bifunctional hydrocracking catalyst, preferably said non-sulphided bifunctional catalysts comprising at least one or more metal(s) selected from noble metals of Group VIII, more preferably at least one or more metal(s) selected from Pt and/or Pd, and at least one or more acidic porous material(s). Non-sulphided bifunctional catalysts are preferred because they do not require sulphidation during operation for maintaining their activity, and hence the sulphur content of various process streams and products may be kept low and less efficient HS separation and recovery is needed. Especially non-sulphided bifunctional catalysts comprising noble-metals may be active at lower temperatures and show higher selectivity for isomerisation reactions, compared to suiphided catalysts, but are sensitive to deactivation by H2S. Particularly for the hydrocracking reactions in the second reaction section/reactor, bifunctional HC catalysts are beneficial because they have in addition to cracking activity also at least some isomerisation activity, and may be particularly efficient in effective cracking. As further advantage, bifunctional hydrocracking catalysts comprising at least one or more metals selected from Group VIII noble metals, preferably Pt and/or Pd, have been found to provide at relatively low temperatures a high activity compared to HC
O catalysis comprising non-noble metais, and thus better control of thermal cracking. At low
S temperatures, the thermodynamic equilibrium tends to shift towards dearomatisation, thus
O reducing aromatics formation by side reactions. Providing the second reaction
S section/reactor with a bifunctional HC catalyst may also achieve an isoparaffin content (wt-
I 30 % isoparaffins of the total weight paraffins) in the hydrocracking effluent that is not > necessarily significantly lower than in the hydroisomerisation effluent, or may be the same
S or even higher.
N According to certain preferred embodiments, the present gasoline fuel component is x obtainable by a process comprising subjecting an oxygenated hydrocarbon feed comprising at least one or more of vegetable oil, animal fat and/or microbial oil to hydrodeoxygenation, followed by gas-liquid separation, to provide a paraffinic hydrocarbon feed comprising at least 60 wt-% paraffins of the total weight of the paraffinic hydrocarbon feed, of which paraffins at most 30 wt-% are i-paraffins: subjecting the paraffinic hydrocarbon feed in a first reaction section, preferably in a first reactor, to hydroisomerisation in the presence of a hydroisomerisation catalyst to obtain ahydroisomerisation effluent; subjecting a second reaction section feed comprising at least a portion of the hydroisomerisation effluent optionally comprising a recycle stream, to hydrocracking in a second reaction section, preferably in a second reactor, in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent; subjecting the hydrocracking effluent to fractionation and recovering from the fractionation at least a gasoline fuel component, and optionally an aviation fuel component and/or the recycle stream preferably having a T5 temperature (5 vol-% recovered, EN ISO 3405-2019) of 270 *C or higher.
The prevailing component in the paraffinic hydrocarbon feed is n-paraffins. However, the presence of a certain amount of i-paraffins in the paraffinic hydrocarbon feed may still be beneficial. Compared to otherwise similar feeds but without i-paraffin content, paraffinic hydrocarbon feeds containing a certain amount of i-paraffins may achieve a hydroisomerisation effluent with a higher content of multiple-branched i-paraffins.
Preferably, the paraffinic hydrocarbon feed of the present disclosure comprises at least 70 wt-%, preferably at least 80 wt-%, more preferably at least 90 wt-% hydrocarbons having a carbon number within a range from C12 to C30, even more preferably within a range from
C14 to C22, of the total weight of the paraffinic hydrocarbon feed. These feeds allow good yields of two or more fuel components of different kinds, and are readily available for example from conventional hydrodeoxygenation processes of vegetable oils, animal fats, and/or microbial oils, comprising fatty acids. Paraffinic feeds on the heavier side are & obtainable e.g. from HDO of oil from energy crops such as Brassica species, algal oils, a crude tall oil (CTO), tall oil fatty acids (TOFA), and/or tall oil pitch (TOP). = Presence of multiple-branched i-paraffins in the hydroisomerisation effluent may be ? considered beneficial as it may contribute beneficially to the degree of effective cracking in s 30 the hydrocracking step. When a desired degree of effective cracking, particularly to C8-C14
S hydrocarbons but also to lighter non-gaseous hydrocarbons, is achieved in the
N hydrocracking step at milder operating conditions, excessive cracking may be avoided, and < formation of gaseous hydrocarbons reduced. Also, an increased content of multiple- branched i-paraffins in the hydroisomerisation effluent may be considered beneficial in that it may provide improved RON to the gasoline fuel component, and improved cold properties to the optionally recovered at least one or more further fuel component(s) such as aviation fuel component and/or diesel fuel component. Without being bound to any theory, it is believed that a muitiple-branched i-paraffin is more likely to form two branched paraffin molecules upon cracking in the hydrocracking step instead of one branched and one n- — paraffin, hence increasing the i-paraffin content of the hydrocracking effluent relative to n- paraffin content. The same can be seen also downstream in the products recovered from fractionation and in an optionally recovered recycle stream.
According to certain embodiments, the first reaction section for hydroisomerisation and the second reaction section for hydrocracking may be situated in one and the same reactor, e.g in separate catalyst beds with appropriate equipment thereto. According to certain other embodiments, the first reaction section for hydroisomerisation is in a first reactor and the second reaction section for hydrocracking is in a second reactor. Having the hydroisomerisation section in a first reactor and the hydrocracking section in a second reactor provides advantages i.e. in process design, process controls, and maintenance.
Preferably, the at least a portion of the hydroisomerisation effluent subjected to hydrocracking comprises at least 50 wt-%, further preferably at least 60 wt-%, more preferably at least 70 wt-%, even more preferably at least 80 wt-% isoparaffins of the total amount of paraffins in the at least a portion of the hydroisomerisation effluent, and optionally multipie-branched isoparaffins at least 5 wi-%, preferably at least 10 wt-%, more preferably atleast 15 wt-%, even more preferably at least 20 wt-%, and typically at most 70 wt-%, of the total amount of paraffins in the at least a portion of the hydroisomerisation effluent.
Typically, the at least a portion of the hydroisomerisation effluent has a cloud point less than 0°C, preferably less than -5°C, more preferably less than -8°C, even more preferably less than -10°C, or less than -15°C (ASTM D 5771-17). n 25 — Hydrocracking of at least a portion of the hydroisomerisation effluent increases the yield of
S non-gaseous cracking products, particularly C8-C14 but also lighter non-gaseous oO hydrocarbons, contributing to yield of the gasoline fuel component. As the feed to the = hydrocracking may contain elevated i-paraffins content, and elevated multiple-branched i- ? paraffins content, the present inventors have found that with the hydrocracking it is possible s 30 — to yield further i-paraffins instead of decreasing their amount, without excessive cracking to
S less valuable light C1-C3 hydrocarbons. 3 The advantageous hydrocarbon composition of the present gasoline fuel component,
N specifically in relation to carbon number distribution and content of i-paraffins and n- paraffins, is demonstrated also in end use as beneficial combustion in engines. When studied in laboratory conditions, characteristics correlating with properties desired for fuels are e.g. the shape of the distillation curve and distillation characteristics. The T10 and T90 temperatures and difference there between immediately reveal to a skilled reader gasoline's suitability to spark-ignition engines and predicted performance therein. Hence, according to — certain embodiments, here is provided a gasoline fuel component, wherein the difference between T90 temperature (90 vol-% recovered, ASTM D7096-19) and T10 temperature (10 vol-% recovered, ASTM D7096-19) is at least 60 *C, more preferably at least 70 *C, even more preferably at least 80°C or at least 100°C, for example within a range from 60 to 140 °C. Preferably, the gasoline fuel component has a T90 temperature (90 vol-% recovered,
ASTM D7096-19) within a range from 95 to 150°C, preferably within a range from 95 to 140°C, more preferably within a range from 95 to 130°C, so as to positively contribute to the octane rating of the gasoline fuel component, and to allow recovery of an aviation fuel component in high yield from the same production process.
Other characteristics followed for gasoline components are related to volatility, vapor — pressure and flash point. Typical measures reflecting said characteristics include E70 and
E150 values. For a gasoline composition, the E70 value defines the percentage (vol-%) evaporated at 70 C at standard atmospheric pressure. A standardized method for determining E70, as well as E100 and E150 values, for a gasoline composition is defined in EN ISO 3405:2011. Due to the carbon number distribution and content of i-paraffins and — n-paraffins in the present gasoline fuel component, blending is not limited by the vapor pressure.
According to a further aspect, the gasoline fuel component may be used in a gasoline fuel composition. The higher i-paraffin content and enhanced i-paraffin profile contribute to improved RON, which allows the present gasoline fuel component to be incorporated in higher amounts in gasoline fuels, compared to e.g. biomass-derived transportation fuel & suitable for use in spark-ignition engines currently commercially available, such currently
N commercially available fuel having a lower RON. Compared to aromatics-containing blend = components the present gasoline fuel component causes less emissions. Additionally, the > present gasoline fuel component may help to increase the bio-content of the gasoline fuel
E 30 composition. Futhermore, each of increased i-paraffin content, increased weight ratio of i-
O paraffins to n-paraffins, and increased weight ratio of multiple-branched i-paraffins to n- : paraffins may help to lower the viscosity of the gasoline fuel component, thereby improving
N mixing and blendability with further components to be included in the gasoline fuel
N composition.
Compared to ethanol, which is currently the prevailing bio-component blended to gasoline compositions, the present gasoline component is less hygroscopic. Further, in distillation of gasoline blends, ethanol as a blending component causes a turn to a steeper slope at about 70 °C and hence produces a notable angle to the distillation curve leading to challenges in meeting the requirements for gasoline compositions e.g. as specified in EN228:2012 amended 2017, whereas the present gasoline fuel component in blends may provide almost linear distillation curve. Contrary to ethanol and other oxygenates, there are no regulatory blending restrictions for paraffinic blend components, like the present gasoline fuel component. Therefore, the present gasoline fuel component is a highly desired alternative blending component for gasoline fuels, and foreseen beneficial both for the production and the end user of the gasoline fuel compositions.
Beneficial vapor pressure characteristics of the present gasoline fuel component enable the use of less expensive and light blend components, such as butane in a gasoline fuel composition, which would not be an option if another component having higher vapor pressure, such as ethanol, was used as the bio-component.
When used in a gasoline fuel composition, the present gasoline fuel component may be blended with at least one or more further component(s). These may originate for example from various sources and/or hydrocarbon refining processes, typically recovered therefrom by distillation. Examples of such processes comprise FCC, reformation, alkylation, pyrolysis, steam cracking, hydrodeoxygenation, hydrodesuiphurisation, isomerisation, or combinations thereof. Hence, in addition to the present gasoline fuel component, the gasoline fuel composition may comprise at least one or more of alcohols, ethers and/or hydrocarbon cut(s), preferably at least one or more of methanol, ethanol, propanol, i- propanol, butanol, i-butanol, tert-butanol, pentanol, i-pentancl, MTBE, ETBE, DIPE, TAME,
TAEE, butane, alkylate gasoline, isomerate, raffinate, FCC gasoline, reformate, pygas & and/or light straight-run (LSR) gasoline. Especially good gasoline fuel compositions,
N regarding high octane rating and biogenic carbon content, are obtainable when maximum = amount of biogenic oxygenated gasoline fuel component(s), preferably biogenic ethanol, as > allowed by the reguired maximum oxygen content, and maximum amount of the renewable
E 30 — gasoline fuel component as allowed by the required minimum octane rating, are blended
O with fossil hydrocarbon cut(s). The gasoline fuel composition may further comprise at least 3 one or more additive(s), preferably at least one or more of antioxidant(s), stabilizer(s),
N detergent(s), corrosion inhibitor(s), friction modifier(s), metal deactivator(s), and/or fuel
N dye(s). Blends containing more than two further components are typical Exemplary gasoline fuel compositions may comprise the present gasoline fuel component, ethanol,
alkylate gasoline, antioxidant(s) and stabiliser(s); or the present gasoline fuel component, ethanol, LSR gasoline, antioxidant(s), stabiliser(s), and detergent(s); or the present gasoline fuel component, MTBE, pygas, FCC gasoline, antioxidant(s), stabiliser(s), friction modifier(s), and detergent(s), just to name a few exemplary gasoline fuel compositions.
According to certain embodiments, blending the gasoline fuel component provides a gasoline fuel composition fulfilling the requirements for gasoline fuels set in Directive 2009/30/EC, and optionally in EN228:2012 amended 2017.
According to certain embodiments, said gasoline fuel composition comprises the present gasoline fuel component in an amount from 1 to 25 vol-%, preferably from 1 to 20 vol-% of the total gasoline fuel composition volume. When the present gasoline fuel component has a high bio-content, the gasoline fuel component alone provides significant bio-content to the gasoline fuel composition. The bio-content may be further enhanced when the gasoline fuel composition comprises the present gasoline fuel component in an amount from 1 vol-% to 25 vol-%, preferably from 1 voi-% to 20 vol-% of the total gasoline fuel composition volume and up to 20 vol-% or up to 10 vol-% of ethanol, preferably bioethanol, of the total gasoline fuel composition volume. For such gasoline fuel compositions, even as high as 45 vol-% of the components may then be renewable providing a biogenic carbon content (EN 16640 (2017)) of more than 40 wt-% based on the total weight of carbon (TC) in the gasoline fuel component. A particularly promising gasoline fuel composition comprises the present gasoline fuel component in an amount of about 10 vol-% and about 10 vol-% bioethanol of the total gasoline fuel composition volume.
In addition to the usability in gasoline fuel compositions, the present gasoline fuel component is suitable for a wide range of various other uses, such as in feedstocks for industrial conversion processes, preferably in thermal cracking feedstocks and/or in n 25 catalytic cracking feedstocks, in solvents, in carriers, in dispersant compositions, in
S demulsifiers, in extractants, in detergents, in degreasing compositions, in cleaners, in oO thinners, in penetrating oils, in anticorrosion compositions, in multipurpose oils, in metal o working, in agriculture, in construction, in electronics, in medical appliances, in compositions
I for car, electrical, textile, packaging, paper and/or pharmaceutical industry, and/or in s 30 manufacture of intermediates therefor. The elevated isoparaffin to n-paraffin ratio of the
S present gasoline fuel compositions may lower viscosity, and improve pumping and mixing
O characteristics, and blendability, that are generally desired and beneficial properties for a
O wide range of uses, and particularly for uses involving spraying, injecting and/or admixing with other ingredients. Due to generally meeting the most important specifications for light naphtha and/or gasoline, that are commonly used as high-volume industrial feedstocks, the present gasoline fuel compositions can be used in the same applications without requiring changes to the existing equipment or facilities. Use of the present gasoline fuel components is particularly preferred in thermal cracking feedstocks and/or in catalytic cracking feedstocks, for producing olefinic monomers, particularly ethylene, and/or propylene, as the very low cyclics’ content helps to reduce formation of coke-forming aromatics, very high paraffin content helps to improve conversion to light olefins, even at less severe cracking conditions, and the high i-paraffin content is foreseen to favor generation of favorable propylene to ethylene product ratios in these processes.
Schematical presentation of the process — Fig. 1 schematically shows a process according to an example embodiment for producing the present gasoline fuel component. in Fig. 1, oxygenated hydrocarbon feed 110 is fed to a HDO reactor 120 in which it is subjected to hydrodeoxygenation in the presence of a HDO catalyst 130 to obtain a hydrodeoxygenation effluent (HDO effluent) 140. The obtained HDO effluent 140 is subjected to gas-liquid separation 150 to separate from the HDO effluent at least compounds that are gaseous at NTP 160 to obtain a degassed HDO effluent 170, which is the paraffinic hydrocarbon feed as herein defined. The degassed HDO effluent 170 is then fed to a first reactor 180 in which the degassed HDO effluent 170 is subjected to hydroisomerisation in the presence of a hydroisomerisation catalyst 190 to obtain a hydroisomerisation effluent (Hi effluent) 200. The obtained HI effluent 200 is subjected to gas-liquid separation 210 to separate from the HI effluent 200 at least compounds that are gaseous at NTP 220 to obtain a degassed HI effluent 230. in Fig. 1, the degassed H! effluent 230 is fed to a distiliation unit 240, that may comprise a single column, or prefractionation and main distillation columns, from which several streams or cuts are obtained. From the distillation in Fig. 1, a gasoline fuel component 250 and an aviation fuel component 260 and/or a diesel fuel component 270 are recovered. Further, a recycle stream 280 having a & T5 boiling point of 270 °C or higher is separated. A second reaction section feed comprising
N the recycle stream 280 as the at least a portion of the HI effluent is in Fig. 1 fed to a second = reactor 290 in which it is subjected to hydrocracking in the presence of a hydrocracking > catalyst 300 to obtain a recycle effluent (hydrocracking effluent) 310. In Fig. 1, the recycle
E 30 effluent 310 is subjected to gas-liquid separation 320 to separate from the recycle effluent
O 310 at least compounds that are gaseous at NTP 330 to obtain a degassed recycle effluent 3 340. The degassed recycle effluent 340 is then fed as a co-feed with the degassed Hi
N effluent 230 to the distillation unit 240 for fractionation. In certain embodiments yet another
N portion of the H! effluent 200 or 230 may be fed as a co-feed 500 with the recycle stream
280, i.e. as part of the second reaction section feed, to hydrocracking in the second reactor 290.
Fig. 2 schematically shows a process according to another example embodiment for producing the present gasoline fuel component. In Fig. 2, oxygenated hydrocarbon feed 110 is fed to a HDO reactor 120 in which it is subjected to hydrodeoxygenation in the presence of a HDO catalyst 130 to obtain a hydrodeoxygenation effluent (HDO effluent) 140. The obtained HDO effluent 140 is subjected to gas-liquid separation 150 to separate from the HDO effluent at least compounds that are gaseous at NTP 160 to obtain a degassed HDO effluent 170, which is the paraffinic hydrocarbon feed as herein defined.
The degassed HDO effluent 170 is then fed to a first reactor 180 in which the degassed
HDO effluent 170 is subjected to hydroisomerisation in the presence of a hydroisomerisation catalyst 190 to obtain a hydroisomerisation effluent (HI effluent) 200.
The obtained HI effluent 200 is subjected to gas-liquid separation 210 to separate from the
HI effluent 200 at least compounds that are gaseous at NTP 220 to obtain a degassed HI effluent 230. In Fig. 2, the degassed Hi effluent 230 is fed to a second reactor 290 in which it is subjected to hydrocracking in the presence of a hydrocracking catalyst 300 to obtain a hydrocracking effluent 350. The hydrocracking effluent 350 is subjected to gas-liquid separation 360 to separate from the hydrocracking effluent 350 at least compounds that are gaseous at NTP 370 to obtain a degassed hydrocracking effluent 380. In Fig. 2, a second reaction section feed comprising the degassed hydrocracking effluent 380 is fed to a distillation unit 240, that may comprise a single column, or prefractionation and main distillation columns, where itis fractionated into several streams or cuts. From the distillation in Fig. 2, a gasoline fuel component 390, and an aviation fuel component 400 and/or a diesel fuel component 410 are recovered. Further, a recycle stream 420, preferably having a T5 boiling point of 270 °C or higher may be separated. In Fig. 2, the recycle stream 420
O may be fed to the second reactor 290 to hydrocracking as a co-feed with the at least a
S portion of the degassed HI effluent 230, i.e. as part of the second reaction section feed. In
O certain embodiments yet another portion of the HI effluent 200 or 230 may be fed as a co-
S feed 500 with the hydrocracking effluent 350 or 380 to the fractionation.
E: 30 EXAMPLES
E Example 1 — Production of present gasoline fuel components
N The gasoline fuel components studied herein were recovered from test runs, where three
N different hydrocracking (HC) feeds (feed A, B, and C) were obtained by subjecting two different types of fatty feedstocks to hydrodeoxygenation (HDO) and gas-liguid separation to obtain paraffinic hydrocarbon feed comprising >95 wt-% paraffins of the total weight of the paraffinic hydrocarbon feed, said paraffinic hydrocarbon feed further subjected to hydroisomerisation (Hi) of different severity. A fraction of the hydroisomerisation effluent obtained by degassing the hydroisomerisation effiuent, or by recovery of just a bottom fraction of the hydroisomerisation effluent, was hydrocracked, followed by degassing the effluent from hydrocracking. A renewable aviation fuel component was recovered from the thus obtained hydrocracking effluent as the main product, and at least a gasoline fuel component as a further product of particular interest here. For one of the hydrocracking effluents (test run 8), a second fractionation was conducted in an optimised way so as to increase the aviation fuel component yield (test run 8 with optimised fractionation, TR80).
Details of the hydrocracking feeds are given in Table 1, and Table 2 shows process details for the hydrocracking as well as approximate boiling point ranges and yields of the gasoline fuel components.
Table 1. Details of the hydrocracking feeds. 1 ] HC Feed B HC Feed A HC Feed C
Animal fat/ vegetable |Animal fat/ vegetable |Heavy vegetable oil/ oil base subjected to |oil base subjected to |animalfat base
HDO, high severity HDO, low severity HI, |subjected to HDO,
HI, degassing and degassing and medium severity HI recovery of bottom recovery of bottom and degassing fraction as HC feed — | fraction as HC feed
Cloud point, *C -30 -11 -27 (ASTM D 5771-17)
Density at -15°C, |788 786 779 kg/m? (EN ISO 12185-1996) & IBP to FBP, °C 284 to 327 286 to 317 78 to 344
N (ENISO3405) oO
N T5; T10 to TSO, °C (292; 293 to 300 294; 295 to 301 208; 251 to 323 a (ENISO3405)
E Paraffins, wt-% nP 3 wt-%; total iP nP 13 wt-%; total iP nP 5 wt-%; total iP e (GCxGC-FID/ 97wt-%; multi-iP 87wt-%; multi-iP 23wt- | 94wt-%; multi-iP 2 GCxGC-MS) 64wt-%; C15-C18 %: 59wt-%; C15-C22
N (each present): 94wt- |C15-C18 (each (each present): 88 < % in total present): 96wt-% in wt-% in total tota!
In Table 1, nP denotes n-paraffins, iP i-paraffins, and multi-iP denotes multiple-branched i- paraffins.
Table 2. Process details for test run conditions in hydrocracking, cloud points of degassed hydrocracking effluents, approximate boiling point ranges and yields of the gasoline fuel components (G) (as wt-% of the degassed HC effluent).
Test | HC HC conditions Effluent's | Yield of G, wt-%| Approx. G G
Run | Feed cloud boiling sample point, *C point range | code
B | 348 ”C, 40 bar, WHSV -79 24.7 IBP to ca G1 0.8 1/h, Ha 300 nL/L 150 °C
A |348*C, 40 bar, WHSV -78 29.7 IBP to ca G2 0.8 1/h, Ha 300 nL/L 150 °C 80 B | 348 °C, 40 bar, WHSV -79 11.4 IBP to ca G3 0.8 1/h, Ha 300 nL/L 100 °C 3 C | 345 °C, 40 bar, WHSV -57 8.4 IBP toca G4 1.3 1/h, H2 360 nL/L 120 °C 4 C | 345 °C, 40 bar, WHSV -83 13.9 IBP toca G5 0.6 1/h, H2 450 nt/L 120 °C 5 C | 350 °C, 40 bar, WHSV -57 13.7 IBP to ca G6 1.3 1/h, H2 225 nt/L 150 °C 6 C | 350 °C, 40 bar, WHSV <-95 25.5 IBP to ca G7 0.6 1/h, H> 450 nU/L 150 °C
The hydrocracking catalyst was a non-sulphided bifunctional hydrocracking catalyst comprising Pt on a zeolite/zeolite-type material in all test runs. When the feeds reported in
Table 1 were subjected to the hydrocracking conditions reported in Table 2, said catalyst had not only cracking but also isomerizing activity.
O
S 10 Gasoline fuel components were generated in good yields, generally the yields being higher
O at higher hydrocracking temperature, at lower WHSV and/or with higher end points as
O expressed e.g. by T95 or FBP.
O
= Example 2 — Chemical composition and distillation characteristics of present a e gasoline fuel components oS ©
O 15 Gasoline fuel components G1-G7 recovered in Example 1 were evaluated based on
O hydrocarbon composition (Tables 3 and 4) and distillation characteristics (Table 5).
Comparison was made to a conventional paraffinic gasoline component (reference gasoline, RG), obtained by subjecting a fatty feedstock to HDO, HI of medium severity,
degassing and fractionation, i.e. without subjecting to hydrocracking. Hydrocarbon composition analysis was conducted with a detailed hydrocarbon analysis, comprising individual component identification (as to hydrocarbon groups [i-paraffins, n-paraffins, naphthenes, aromatics, olefins] and carbon numbers [C#]). Examples of the volumetric shares as analysed are given in Tables 3 and 4. The methods used were in-house methods adapted from standard methods ASTMD6729 and ENISO22854.
In addition to volumetric shares of i- and n-paraffins and multiple-branched i-paraffins, further characteristics were calculated such as i- to n-paraffin ratio and average carbon numbers for C4-C9 i- and n-paraffins (Tables 3 and 4). The average carbon numbers Cavg for C4-C9 range i- and n-paraffins were calculated multiplying the volumetric share for each carbon number C# vol, further making a distinction based on hydrocarbon groups (i-paraffin, n-paraffin). From these, the average carbon numbers for C4-C9 range i- and n-paraffins were calculated using the following equation. (i or n)P(C4 — C9)avylCt < 4 (i or n) PCA vol si (i or n)PC5 vol + 6 = "(or PCA Cool > (ior mP(C4 — C9)vol , (i or n)PC6 voi ey (i or n)PC7 vol ry (i or n)PC8 vol +o (ior n)P(C4— C9)vol — (lor m)P(Ch— C9)wol — (ior n)P(C4— CI) vol (i or n)PC9 vol (i or n)P(C4— €9)vol
As an example of said calculations, the average carbon number 5.8 for C4-C9 n-paraffins and 7.0 for C4-C9 i-paraffins in sample G7 were calculated as follows: — 4 saCk = 3 086 L217 6a ele 7, 1 18 29 19. 92 n = paraf avger = 3+ 3045 tA mt as 2645 Teas TP Teas 77645 = 5.8
Co aC = 4 2.67 s 8.10 + 6 1356 1831 5 19.55 9 8.73 = 70 = paraf avgCh = 4*5TT3 + "GA Tm S TB TY ET
Average carbon numbers for other sampies were calculated accordingly.
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O
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I a a
O oS ©
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Table 3. Compositional characteristics of test run gasoline fuel components G1-G3 (derived from HC feed A or B), and paraffinic reference gasoline component RG as determined by
GC-FID/GC-MS.
Sam | G1 (vol-%) IBP to | G2 (vol-%) IBP to | G3 (vol-%) IBP to | RG (vol-%) ca. 47 ple ca.150*%€ ca. 150% ca. 100*€ to ca. 170°C . . . NO .
C# iP nP I NOA | IP nP | NOA | iP nP A iP nP | NOA soon) [| ke | | 11 “+ | saajaa] |asrjam] ow iss] | jom] - [3 | rasjsaa] [9202] [rela | voo|morj os 12.03 13.40 2190] 10.42] 03 | 1988] 1445] 23 7 | [sar] 430 | 02 [107s] 446] 02 [2008] 120] 07 | osaltaan] 22 8 |1040]200] 02 [1745 278 25 [1107] 004] 05 [1118] 398 | 10- a [2210 [00 jaa] | [osa] | |sasjomjos oles] | | | | | | | [1osja20] on ov 1 |!!! | | | | [osa] 008] 00]
R 1 1 1 | Lp] a eo 1 1 1 | | |. | [emjoot]
R I 1 11 |] | | | fees] sp pp] jom]
Tot | 100] 273 | 08 [osa | 301] 20 | 708] 270] 15 | 519 |415 | 05
Ava.
CF | 70 | 58 6.7 | 5.5 66 | 59 6.9 | 63 0 C4-9
N
N iC8/
EN nC8 5.5 6.3 18.2 2.8 2 iC6- - 8/n 3.4 3.7 3.4 1.4 a C6-8
O .
O i
N
O C6-9 = n.a. = not analysed in Table 3, NOA column denotes sum amounts of naphthenes, olefins and aromatics, C# denotes carbon number, C6-9 m-iP indicates amount of multiple-branched i-paraffins in the
C6-C9 range, average C# C4-9 denotes calculated average carbon number for the C4-C9 range n-paraffins and i-paraffins.
Table 4. Compositional characteristics of test run gasoline fuel components G4-G7 (derived from HC feed C) as determined by GC-FID/GC-MS.
Sam G4 (vol-%) G5 (vol-%) IBP to | G6 (vol-%) IBP to G7 (vol-%) ple IBP to ca. 120°C ca. 120°C ca. 150°C IBP to ca.150°C “or |e [ee [Noa] & | ne [son] | ne [von] [ np [non [e] | jon] | [16] | jos] + [sere] [aves] [ansa] [oojam] 3 | 1100] 1023] 00 | 010] 760 00 | a20] 080] 00 |810 021 00 8 [1800|1019] 03 1852) 780 | 03 [1329] 648 | 02 [1980] 618 | 02 7 [2080] 802 | 06 [2116] sas | 07 [1821] 525] 00 [1931] 491 | 07 “a [er [os | 12 1828] 173 | 18 1897) 314 10 [1088] 200] 12 s [057 008 | 00 | 104] 008 00 | 790] 012] 02 [73 [020] 03. | om 001 | 00 [018 001 | 00 01s 001 | ooo] | -
Cn fo] Jeo jom] | [oo] | joo] | -
R 1 1 1 1! |. joo]
Tor [620] 369] 21 | 001 | 292 | 20 |694 | 200] 20 | 711284 | 24
Ava.
CF | 63 | 55 6.7 | 57 6.9 | 5.8 7.0 | 5.8
C4-9
O
N .
N iC8/ 20.6 10.6 6.0 6.7
O nC8 o iC6- © 8/n 2.8 36 3.4 3.7 = C6-8 a 2
O iP
S
2
N m-IP in Table 4, NOA column denotes sum amounts of naphthenes, olefins and aromatics, C# denotes carbon number, C6-9 m-iP indicates amount of multiple-branched i-paraffins in the
C6-C9 range, average C# C4-9 denotes calculated average carbon number for the C4-C9 range n-paraffins and isoparaffins.
Table 5. Distillation characteristics of gasoline fuel components G1-G7 (given as temperatures, °C, at which specified vol-% recovered, according to ASTM D7096-19), as well as boiling ranges as FBP minus IBP, and T90 minus T10.
From Tables 3 and 4, it can be seen that gasoline fuel components G1-G7 have significantly higher ratios of C8 i-paraffins to C8 n-paraffins, from almost double to sevenfold, compared = 10 tothe paraffinic reference gasoline RG, while at the same time containing significant amount
N of C8 paraffins. Similarly, the gasoline fuel components G1-G7 have significantly higher > ratios of C6-C8 i-paraffins to C6-C8 n-paraffins, at least double, compared to the paraffinic a reference gasoline RG, while at the same time mainly containing C6-C8 paraffins. The
E gasoline fuel components G1-G7 have also moderate average carbon numbers for C4-C9 en 15 range i-paraffins, being above 6.0 units, and low average carbon numbers for C4-C9 range 3 n-paraffins, being below 6.0 units, and at least 0.7 units smaller than the respective average
N carbon numbers for C4-C9 i-paraffins. The measured samples of the gasoline fuel
N components according to the present disclosure have high multiple-branched C6-C9 i- paraffin contents, >6.0 %, even >10 %, compared to <5.0 % of the reference gasoline RG,
while at the same time mainly containing C4-C9 i-paraffins. Also, the amount of n-hexane is much lower in the gasoline fuel components according to the present disclosure compared to the reference gasoline RG. From Table 5, it can be seen how gasoline fuel compositions G1-G7 have relatively linear distillation behavior, which is beneficial for example for burning characteristics. The boiling ranges reported in Table 5 show that the gasoline fuel components do not represent narrow cuts, but that vast majority of the component volume boils over a fairly wide temperature range. The gasoline fuel components are thus recoverable with higher yields.
Example 3 - Octane ratings of present gasoline fuel components
The properties listed in Tables 3 and 4 are closely linked to octane rating of the gasoline fuel components. More specifically, higher degree of isomerisation, higher amount of i- paraffins and lower average carbon numbers in the C4-C9 range paraffins, were observed to result in higher octane ratings. Higher octane ratings are desired for use in gasoline fuel compositions for use as liguid transportation fuels.
Blend RON (ENISO5164-2014 corresponds to ASTMD2699-18) and blend MON (ENISO5163-2014 corresponds to ASTMD2700-19) were determined from the paraffinic reference gasoline component RG, and from three test run samples G3, G5, G7, produced under similar conditions, the main difference of said test run samples being the end cut points (about 100°C, 120 °C and 150 °C) (Table 6).
The gasoline fuel component quality was noted to be impacted at least by the process parameters. Higher temperature and lower WHSV in the hydrocracking facilitated higher i- paraffin content and slightly lower average carbon numbers in the C4-C9 range paraffins, when comparing to samples with similar distillation range. By measure of the set guality parameters, better gasoline fuel component was obtained at higher hydrocracking = 25 temperatures and lower WHSV. Due to low volumes of the samples, the octanes were
N determined from blends with a commercial gasoline component havina high i-paraffin > content, referred to as “2™ component”. The blending octane numbers for bRON samples
S were calculated using the following equation: 2 bRONsample = oo a 00
O
S
N 30 Theblend RON and MON for the sample G5 of the gasoline fuel component (120 *C cut)
N were 66.7 and 55.5, respectively. The corresponding values for the sample G7 (150 °C cut) were 59.1 and 56.7. Sample G7 had higher i-paraffin content and i- to n-paraffin ratio, but the average carbon number was higher for both the i- and n-paraffins. The average carbon number in the C4-C9 range paraffins, especially of C4-C9 n-paraffins, seemed to have a bigger impact on the RON than the i-paraffin content. The reference gasoline RG properties describing the product quality were inferior to the test run gasoline fuel components. The measured test run gasoline fuel components (samples G3, G5, and G7) had significantly higher blend octane ratings than the reference gasoline RG (PRON = 46.8 and bMON = 45.3), determined from similar blend using the same methods.
Comparing the BRON and bMON results of samples derived from hydrocracking feeds B and C reveals the effect of the characteristics of the hydrocracking feeds (reported in Table 1) and of the chemical composition of the gasoline fuel components (reported in Tables 3 and 4) on the gasoline fuel component guality in terms of octane numbers (reported in Table 6). The most promising hydrocracking feed B derived gasoline fuel component (G3) was compared to the two hydrocracking feed C derived gasoline fuel components (G5 and G7), the gasoline fuel component samples were obtained from similar process conditions (with slight variation in the hydrocracking temperature). The paraffin contents were very similar between the samples despite varying end cut points of the gasoline fuel components. The
C4-C9 i-paraffin content was in the range from 68 to 71 vol-%, and n-paraffins from 26 to 29 vol-%. The relative multiple-pranched i-paraffin content was increased with increasing end cut point of the gasoline fuel component sample, suggesting that the longer paraffins underwent higher degree isomerisation in the process. Comparison was again made to the same paraffinic reference gasoline RG, which had lower C4-C9 i-paraffin content of about 49 vol-%, and higher n-paraffin content of about 42 vol-%.
Table 6. Octane numbers and distillation ranges of the gasoline fuel components G3, G5,
G7, and the reference gasoline RG.
S gasoline & :
T approx. (°C) 100 120 150 s
E 25 ThebRON differences can be explained in part by assessing the carbon number distribution
N (Tables 3 and 4). However, the analyzed samples G3, G5 and G7 have similar low C4-C9
N n-paraffin average carbon numbers (5.7-5.9) while more variations can be seen in the C4-
C9 i-paraffin average carbon numbers (6.6-7.0). The reference gasoline fuel component
RG has similar C4-C9 i-paraffin average carbon number as G3, G5 and G7, but far higher
C4-C9 range n-paraffin average carbon number (6.3). Like mentioned above, the RON rating increases with degree of isomerisation and lower carbon number (shorter carbon chain length). Thus, one important differentiating factor between the octane ratings of the gasoline fuel components according to the present disclosure and the reference gasoline fuel components was the average C4-C9 range n-paraffin carbon number. The G3 gasoline fuel component and G7 gasoline fuel component have similar blend octane ratings, although the average C4-C9 range i-paraffin carbon number was lower in G3 gasoline fuel component, this was balanced out with the lower average C4-C9 range n-paraffin carbon number of G7 gasoline fuel component. The C4 content was relatively high with the G5 and
G7 gasoline fuel components, contributing significantly to the average carbon numbers of the C4-C9 range n-paraffins and to the measured octane ratings. With the information at hand, the amount of C4 compounds cannot be attributed to the used hydrocracking feed as the difference might arise from the selected IBPs, influenced e.g. by different degassing — and/or distillation procedures used to obtain the products.
Based on the hydrocracking test runs with the different feeds, it can be said that the feeds have some impact on the gasoline fuel component quality. The gasoline fuel components obtained by the process involving hydrocracking of paraffinic stream having high degree of isomerisation have inter alia far better octane numbers than the paraffinic reference gasoline component. Overall, the test runs have shown that lower WHSV and/or higher temperature at the hydrocracking improve the gasoline fuel component yields, and may also improve the properties for gasoline fuel applications, with less influence by the hydrocracking feed, while lower distillation end point (e.g. T90, 195 and/or FBP) and lower average carbon number of C4-C9 range paraffins, especially of C4-C9 range n-paraffins, can be expected to improve the octane rating. & Various embodiments have been presented. It should be appreciated that in this document,
N words comprise, include, and contain are each used as open-ended expressions with no = intended exclusivity. a
I The foregoing description has provided by way of non-limiting examples of particular s 30 implementations and embodiments a full and informative description of the best mode
S presently contemplated by the inventors for carrying out the invention. It is however clear to
O a person skilled in the art that the invention is not restricted to details of the embodiments
O presented in the foregoing, but that it can be implemented in other embodiments using equivalent means or in different combinations of embodiments without deviating from the characteristics of the invention. Furthermore, some of the features of the afore-disclosed example embodiments may be used to advantage without the corresponding use of other features. As such, the foregoing description shall be considered as merely illustrative of the principles of the present invention, and not in limitation thereof. Hence, the scope of the invention is only restricted by the appended patent claims.
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Claims (20)
1. A gasoline fuel component comprising n-paraffins, monobranched i-paraffins, and multipie-branched i-paraffins, wherein the sum amount of C4-C9 n-paraffins, C4-C9 mono-branched i-paraffins, and C4-C9 — muitiple-pranched i-paraffins is more than 90 wt-% of the tota! gasoline fuel component weight, and wherein the weight ratio of C8 i-paraffins to C8 n-paraffins is at least 4.0, preferably at least
4.5, further preferably at least 5.0, more preferably at least 5.5, even more preferably at least 6.0, and at most 30, and the sum amount of C8 n-paraffins and C8 i-paraffins is at least 5.0 wi-%, preferably at least 5.5 wt-%, more preferably at least 6.0 wi-%, even more preferably at least 7.0 wi-% of the total gasoline fuel component weight.
2. The gasoline fuel component according to claim 1, wherein the gasoline fuel component comprises at least C6, C7 and C8 paraffins and the weight ratio of C6-C8 i- paraffins to C6-C8 n-paraffins is at least 2.7, preferably at least 2.8, more preferably at least
3.0, and optionally the sum amount of C6-C8 n-paraffins and C6-C8 i-paraffins is at least 50 wt-%, preferably at least 55 wt-%, more preferably at least 58 wt-% of the tota! gasoline fuel component weight.
3. The gasoline fuel component according to claim 1 or 2, wherein the weight ratio of C6-C9 multiple-branched i-paraffins to C6-C9 n-paraffins is at least 0.2, preferably at least
0.3, more preferably at least 0.4, even more preferably at least 0.5.
4. The gasoline fuel component according to any one of the preceding claims, comprising at least 50 wi-%, preferably at least 55 wt-%, more preferably at least 60 wt-%, even more preferably at least 65 wt-% C4-C9 i-paraffins of the total gasoline fuel component e weight; and/or at least 5 wt-%, preferably at least 6 wt-%, more preferably at least 7 wt-%, S 25 even more preferably at least 10 wt-%, or at least 11 wt-%, C6-C9 multiple-branched i- O paraffins of the total gasoline fuel component weight.
a 5. The gasoline fuel component according to any one of the preceding claims, wherein E the sum amount of C4-C9 n-paraffins, C4-C9 mono-branched i-paraffins and C4-C9 e multiple-branched i-paraffins is more than 93 wt-%, preferably more than 95 wt-%, more 3 30 preferably within a range from 95 to 99 wt-% of the total gasoline fuel component weight. N
O 6. The gasoline fuel component according to any one of the preceding claims, wherein the bRON of said gasoline fuel component, as determined according to ASTM D2699-18, is at least 51, preferably at least 55.
7. The gasoline fuel component according to any one of the preceding claims, wherein the bMON of said gasoline fuel component, as determined according to ASTMD2700-19, is at least 48, preferably at least 50, more preferably at least 55.
8. The gasoline fuel component according to any one of the preceding claims, wherein the average carbon number of C4-C9 n-paraffins is at most 6.0, preferably at most 5.6, and preferably at least 0.5 units lower, more preferably at least 0.6 units lower than the average carbon number of C4-C9 i-paraffins.
9. The gasoline fuel component according to any one of the preceding claims, wherein the average carbon number of C4-C9 i-paraffins is more than 6.0, preferably at least 6.2, — more preferably within a range from 6.2 to 8.0.
10. The gasoline fuel component according to any one of the preceding claims, wherein the C6 n-paraffin content is at most 11 wt-%, preferably at most 8 wt-% of the total gasoline fuel component weight, and/or the weight ratio of C6 i-paraffins to C6 n-paraffin is at least
1.5, preferably at least 1.7. 11 The gasoline fuel component according to any one of the preceding claims, wherein the biogenic carbon content of the gasoline fuel component, as determined according to EN 16640 (2017), is at least 50 wt-%, preferably at least 70 wt-%, further preferably at least 90 wi-%, more preferably at least 95 wt-%, even more preferably about 100 wt-%, based on the total weight of carbon (TC) in the gasoline fuel component.
12. The gasoline fuel component according to any one of the preceding claims, wherein the difference between T90 temperature (90 vol-% recovered, as determined according to ASTM D7096-19) and T10 temperature (10 vol-% recovered, as determined according to ASTM D7096-19) is at least 60 °C, more preferably at least 70 °C, even more preferably at n least 80 °C or at least 100 °C, such as within a range from 60 to 140 °C. S 25 13. The gasoline fuel component according to any one of the preceding claims, obtainable O by a process comprising S providing a paraffinic hydrocarbon feed comprising at least 60 wt-% paraffins of the z total weight of the paraffinic hydrocarbon feed, of which paraffins at most 30 wt-% are i- > paraffins; E 30 subjecting the paraffinic hydrocarbon feed in a first reaction section, preferably in a N first reactor, to hydroisomerisation in the presence of a hydroisomerisation catalyst to obtain N a hydroisomerisation effluent;
subjecting a second reaction section feed comprising at least a portion of the hydroisomerisation effluent to hydrocracking in a second reaction section, preferably in a second reactor, in the presence of a hydrocracking catalyst to obtain a hydrocracking effluent; subjecting the hydrocracking effluent, and optionally a portion of the hydroisomerisation effluent, to fractionation, and recovering from the fractionation at least a gasoline fuel component, and optionally an aviation fuel component.
14. Use of a gasoline fuel component according to any one of claims 1 to 13 in a gasoline fuel composition.
15. A gasoline fuel composition comprising a gasoline fuel component according to any one of claims 1 to 13.
16. Use according to claim 14 or the gasoline fuel composition according to claim 15, wherein said gasoline fuel composition comprises at least one or more of oxygenated gasoline fuel component(s) and/or hydrocarbon cut(s), preferably at least one or more of ethanol, propanol, i-propanol, butanol, i-butanol, tert-butanol, pentanol, i-pentanol, MTBE, ETBE, TAME, TAEE, butane, alkylate, isomerate, raffinate, FCC gasoline, reformate, pygas and/or light straight-run (LSR) gasoline.
17. Use according to claim 14 or 16 or the gasoline fuel composition according to claim 15 or 16, wherein said gasoline fuel composition fulfills the requirements for gasoline fuels — setin Directive 2009/30/EC, and optionally in EN228:2012 amended 2017.
18. Use according to any one of claims 14, 16 or 17 or the gasoline fuel composition according to any one of claims 15, 16 or 17, wherein said gasoline fuel composition comprises the gasoline fuel component according to any one of claims 1 to 13 in an amount from 1 to 25 %-vol, preferably from 1 to 20 %-vol of the total gasoline fuel composition S 25 volume. O 19. Use of a gasoline fuel component according to any one of claims 1 to 13 in feedstocks S for industrial conversion processes, preferably in thermal cracking feedstocks and/or in z catalytic cracking feedstocks, in solvents, in carriers, in dispersant compositions, in > demulsifiers, in extractants, in detergents, in degreasing compositions, in cleaners, in S 30 thinners, in penetrating oils, in anticorrosion compositions, in multipurpose oils, in metal N working, in agriculture, in construction, in electronics, in medical appliances, in compositions i for car, electrical, textile, packaging, paper, and/or pharmaceutical industry, and/or in manufacture of intermediates therefor.
20. Use according to any one of claims 14, 16, 17, 18 or 19, or the gasoline fuel composition according to any one of claims 15 to 16, or the gasoline fuel component according to any one of claims 1 to 13, wherein the gasoline fuel component or the gasoline fuel composition is additized with at least one or more of antioxidant(s), stabilizer(s), — detergent(s), corrosion inhibitor(s), friction modifier(s), metal deactivator(s), and/or fuel dye(s). O N O N O O O I a a O oS © LO N N O N
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PCT/FI2023/050418 WO2024003468A1 (en) | 2022-06-30 | 2023-06-30 | A process for producing liquid transportation fuel components |
PCT/FI2023/050416 WO2024003466A1 (en) | 2022-06-30 | 2023-06-30 | A hydrocarbon component |
PCT/FI2023/050413 WO2024003463A1 (en) | 2022-06-30 | 2023-06-30 | An aviation fuel component |
PCT/FI2023/050415 WO2024003465A1 (en) | 2022-06-30 | 2023-06-30 | A process for producing liquid transportation fuel components |
PCT/FI2023/050414 WO2024003464A1 (en) | 2022-06-30 | 2023-06-30 | A gasoline fuel component |
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