WO2022243599A1 - Composition intermédiaire à deux composants à indice d'octane renforcé - Google Patents

Composition intermédiaire à deux composants à indice d'octane renforcé Download PDF

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WO2022243599A1
WO2022243599A1 PCT/FI2022/050322 FI2022050322W WO2022243599A1 WO 2022243599 A1 WO2022243599 A1 WO 2022243599A1 FI 2022050322 W FI2022050322 W FI 2022050322W WO 2022243599 A1 WO2022243599 A1 WO 2022243599A1
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component
renewable
gasoline
intermediate composition
alkanes
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Juha KESKIVÄLI
Markku Kuronen
Ulla Kiiski
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Neste Oyj
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    • 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
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof

Definitions

  • the present disclosure generally relates to gasoline fuel compositions comprising prenol, intermediates, production processes and uses thereof.
  • the disclosure relates particularly, though not exclusively, to two-component intermediate compositions for gasoline providing enhanced octane rating through synergy.
  • Commercial gasoline which is fuel for internal combustion engines, is a refined petroleum product that is typically a mixture of hydrocarbons (base gasoline) and additives.
  • Additives are added to the base gasoline to enhance the performance and the stability of gasoline.
  • Said additives comprise for example antioxidants and octane enhancers.
  • Knocking occurs when combustion of the air/fuel mixture in the cylinder does not start off correctly in response to ignition because one or more pockets of air/fuel mixture pre-ignite outside the envelope of the normal combustion front.
  • Anti-knocking agents also known as octane enhancers, reduce the engine knocking phenomenon, and increase the octane rating of the gasoline.
  • Traditional octane enhancers such as tetraethyl lead and methylcyclopentadienyl manganese tricarbonyl (MMT) have been or are being banned in many countries for environmental and health reasons.
  • the anti-knock quality of a fuel is normally rated by its octane number (ON), which can be determined in accordance with one of two protocols on a so-called cooperative fuel research (CFR) engine: Research Octane Number (RON) or Motor Octane Number (MON). Both standards use n-heptane and iso-octane as reference fuels. To date, both values are determined on a standardized CFR engine in accordance with ASTM protocols D-2699 and D-2700, respectively. Both norms were designed to be representative of the mildest (RON) and most severe (MON) operating conditions.
  • the highly reactive n-heptane and highly stable iso-octane are used as surrogate fuels, spanning the octane scale from 0 to 100, respectively.
  • quantifying the octane number of mixtures comprising additional components is challenging because blending interactions are highly non-linear.
  • said non-linear behaviour applies to some other important gasoline specification parameters as well, such as vapor pressure, rendering predicting said characteristics for multi-component compositions demanding.
  • the predominant octane enhancer today on the market is ethanol.
  • the ethanol content in gasoline is nevertheless limited mainly due to maximum oxygen content accepted in gasoline blends, whereby other oxygen containing octane enhancers have gained interest.
  • US10899988B1 disclosed octane boosting properties of alkenols.
  • Exemplary alkenols included prenol (3-methyl-2-buten-1-ol), isoprenol (3-methyl-3-buten-1-ol) and 2-methyl-3-buten-2-ol. They observed that the RON of the prenol-containing fuel blend exceeding the RON of both the neat compound and the base fuel for all RBOBs (reformulated blendstocks for oxygenated blending) into which prenol was blended. They introduced term “octane hyperboosting” to describe this effect to distinguish it from synergistic blending or RON boosting commonly used to describe non-linear RON blending.
  • prenol is a known unsaturated alcohol. It has a neat RON of 94 and a boiling point of 142 °C. Some biomass-based prenol production pathways have been identified.
  • Paraffinic gasoline components derived from raw materials of biological origin provide excellent combustion properties, but have been associated with poor octane values.
  • the present inventors found surprisingly an increasing effective octane boosting property with increasing volume of prenol in renewable paraffinic gasoline component. Thereby the maximum amount of renewable paraffinic gasoline component in gasoline blends can be increased.
  • the experiments conducted, for example, with the 20 vol% addition of prenol to the renewable paraffinic gasoline component (RON 65.4, MON 64.5) gave an impressive 49% boost to RON and 48% boost to MON compared to neat renewable paraffinic gasoline component (RON 43.9, MON 43.6).
  • prenol octane boosting properties in blends with renewable paraffinic gasoline component, contribute to creating higher sensitivity gasoline blends.
  • prenol fits well to the EN228 allowed alcohols due to its appropriate boiling point. Considering energy efficiency, prenol has better heating value than ethanol.
  • a use of prenol and a renewable paraffinic gasoline component as a two- component intermediate composition for gasoline fuel is provided.
  • said two-component intermediate composition is blended with at least one further component to provide a gasoline fuel.
  • Said gasoline fuel may be defined as fulfilling requirements set in Directive 2009/30/EC and optionally EN228:2012 amended 2017.
  • Fig. 1 shows bRON results for prenol when blended with different paraffinic hydrocarbon components.
  • the bRON for prenol increased with increasing prenol share in two-component intermediate compositions comprising a renewable paraffinic gasoline component as the second component.
  • the effect was reversed when another paraffinic component was used instead of the renewable paraffinic gasoline component.
  • Fig. 2 gives the corresponding results for bMON.
  • Fig. 3 provides dry vapour pressure equivalents (DVPE, determined with EN13016- 1 method) for blends of corresponding amounts of prenol and ethanol with the same base gasoline.
  • DVPE dry vapour pressure equivalents
  • bio-component content refers to the share of component of biological origin or a component derived from renewable sources in the two- component intermediate composition.
  • “renewable” refers to objects of bio-origin or derived from wastes.
  • the bio-component content in a gasoline fuel as an end product, is also of interest, especially for regulatory reasons.
  • renewable and fossil components refer to non-renewable fuels and non-renewable energy in contrast to renewable counterparts. Said renewable and fossil components are considered differing from one another based on their origin and impact on environmental issues. Therefore, they are treated differently under legislation and regulatory framework.
  • renewable and fossil components are differentiated from one another based on their origin and information provided by the producer.
  • chemically the renewable or petroleum origin of any hydrocarbons can be determined by isotopic distribution involving 14 C, 13 C and/or 12 C as described in ASTM D6866.
  • gasoline With gasoline, it is here referred to a liquid fuel having a boiling point in the range of 30 to 200° C and comprising hydrocarbons having from 4 to 12 carbon atoms.
  • gasoline there have been attempts to differentiate between "raw" gasoline having inferior properties, such as anti-knock properties from fuel grades having excellent properties and fulfilling requirements set to high octane fuels.
  • gasoline fuel refers to an end-product meeting specifications, such as EN 228:2012 Amended 2017.
  • a gasoline fuel comprises at least one further gasoline component.
  • a two-component intermediate composition refers to a blend of prenol in specified volume contents with a renewable paraffinic gasoline component as defined in this specification. As an intermediate it is eventually blended with at least one further component to provide a gasoline fuel fulfilling requirements set by authorities for traffic gasoline or petrol grade fuels.
  • a gasoline component refers to a stream useful as a blend component which together with other streams contributes to a gasoline fuel as an end product meeting specifications.
  • Prenol (3-methyl-2-buten-1-ol) is a commercially available product.
  • Industrially prenol is produced via a well-established catalytic route from petroleum-derived isobutene and formaldehyde as an intermediate in the production of citral.
  • prenol can also be synthesized from isoprene via several catalytic processes.
  • prenol synthesis precursors can also be produced via renewable routes.
  • prenol is available as a partly or fully renewable variant.
  • Prenol production biologically from glucose uses genetically modified microorganisms. Biological prenol production has only been demonstrated in laboratory-scale batch systems.
  • the renewable paraffinic gasoline component of two-component intermediate composition consists essentially of saturated hydrocarbons.
  • Said renewable paraffinic gasoline component comprises alkanes, which are also referred to as paraffins, more specifically it contains n-alkanes, iso-alkanes and cyclo-alkanes, also referred to as n-paraffins, i-paraffins and cycloparaffins respectively.
  • Reference to renewable C4-C12 n-alkanes, iso-alkanes and cyclo-alkanes is in more detail to renewable C4-C12 n-alkanes, renewable C4-C12 iso-alkanes and C4-C12 renewable cyclo-alkanes.
  • content of any other types of hydrocarbons or oxygenates in said renewable paraffinic gasoline component is negligible, such as below 0.5 vol-% of the renewable paraffinic gasoline component volume.
  • renewable paraffinic gasoline component of the present two-component intermediate composition at least 99 %-vol of said renewable paraffinic gasoline component consists of renewable C4-C12 alkanes selected from renewable n- alkanes, renewable iso-alkanes and renewable cyclo-alkanes, and the ratio of the amount of the renewable C8 n-alkanes to the amount of renewable C8 i-alkanes is from 1 :10 to 1 :2. As per the paraffinic content, it is distinguished from extremely highly isoparaffinic components, such as alkylates.
  • the sum amount of the renewable C4-C12 n-alkanes, iso-alkanes and cyclo-alkanes varies from 99 to 100 vol-% of the total renewable paraffinic gasoline component volume.
  • the sum amount of components other than the alkanes defined above is less than 1 vol- %, preferably less than 0.5 vol-%.
  • Typical components therein comprise less than 0.5 vol-% alkenes, less than 0.5 vol-% C10-C13 n-alkanes, less than 0.5 vol-% C11- C14 iso-alkanes, less than 0.5 vol-% C10-C13 cyclo-alkanes.
  • the renewable paraffinic gasoline component may be very low in aromatic contents, i.e.
  • the aromatic content of the renewable paraffinic gasoline component may be e.g. about 0.1 vol-%, preferably less than 0.1 vol-% or even aromate-free.
  • the renewable paraffinic gasoline component is a hydrotreated renewable paraffinic gasoline component according to above definition.
  • a hydrotreated renewable paraffinic gasoline component may be derived from a glyceride containing feedstock, such as fatty acids or esters thereof, by processes known in the art, and disclosed for example in FI100248B or EP1741768A1.
  • the product therefrom may be further processed and fractionated to provide a renewable paraffinic gasoline component, typically the further fractions comprising at least one of renewable paraffinic diesel, renewable paraffinic aviation fuels, and possibly heavier, such as renewable paraffinic base oil or renewable paraffinic transformer oil.
  • the main product is 2,4-dimethylpentane. Therefore, it is characteristic to these alkylates that the content of C8 i-paraffins of the total alkylate volume may be more than 50 %-wt, more than 60 %-wt or even more than 70 %-wt. At the same time, the alkylate contains relatively low content of any n-paraffins, such that the sum content of C4 to C12 n-paraffins is typically less than 10 %-wt. Such a highly i-paraffinic hydrocarbon composition may be expected to exhibit high octane numbers as such.
  • a two-component intermediate composition for gasoline comprising: prenol in an amount of from 5 to 20 vol-% of the total two-component intermediate composition volume; and the rest of the total intermediate composition volume consisting of a renewable paraffinic gasoline component, wherein at least 99 vol-% of said renewable paraffinic gasoline component consists of renewable C4-C12 alkanes selected from renewable n-alkanes, renewable iso-alkanes and renewable cyclo alkanes, and the ratio of the amount of the renewable C8 n-alkanes to the amount of renewable C8 i-alkanes is from 1 :10 to 1 :2.
  • the blend octane behavior may be characterized as improved blend octane properties, wherein the hydrocarbon component of the two-component intermediate has a relatively low neat octane number.
  • such component boosts the blend octane numbers for prenol, specifically, when the prenol content in said two- component intermediate is from 5 vol-% to 20 vol-%.
  • Such a two-component intermediate composition has a RON of as measured according to ASTM D2699, from 45 to 70. When compared to the RON of the neat renewable paraffinic gasoline component, the 48 % rise with relatively modest prenol content was surprising.
  • the two-component intermediate composition for gasoline comprising from 5 to 20 vol-% of the total two-component intermediate composition volume prenol, and the rest consisting of a renewable paraffinic gasoline component as defined herein, measured surprisingly good blend octane behavior, and at the same time, a notable bio component content.
  • the two-component intermediate composition may have a bio-component content wherein at least 80 vol-%, preferably at least 90 vol-%, more preferably at least 99 vol-% of the carbon of the two-component intermediate composition volume is of renewable origin, determined by isotopic distribution of 14 C, 13 C and/or 12 C as described in ASTM D6866.
  • the prenol is of renewable origin and determined similarly, yielding essentially renewable two- component intermediate composition and hence at least 99 vol-% of the carbon of the two-component intermediate composition volume is of renewable origin.
  • the sum amount of C4-C7 n-paraffins is at least 15 vol-%, preferably at least 20 vol-%, such as from 15 to 45 vol-%, preferably from 20 to 40 vol-% of the total two-component intermediate composition volume.
  • said n-paraffins in a blend with prenol seem to contribute to the octane boost through chemical compatibility of said compounds.
  • the effect yielded by the present two-component intermediates for gasoline show significant improvement.
  • n-paraffins typically represent lower processing degree, and therefore are beneficial to overall economy.
  • the two-component intermediate composition for gasoline can be further adjusted with components or additives meeting requirements set in standards or other regulations.
  • Such an additive e.g. an octane enhancer
  • An example of such procedure may be a use of the two- component intermediate composition, which is blended with ethanol only at a distribution terminal.
  • a gasoline fuel comprising a two-component intermediate composition according to the present disclosure, always provides advantageous gasoline compositions with regard to environmental aspects and requirements since it comprises renewable carbon at least 80 vol-%, preferably at least 95 vol-% and up to 99 vol-%, and the overall gasoline fuel may comprise further renewable components, such as renewable oxygenates.
  • a use of prenol and a renewable paraffinic gasoline component as a two-component intermediate composition for gasoline fuel said two-component intermediate composition comprising: prenol in an amount of from 5 to 20 vol-% of the total two-component intermediate composition volume; and the rest of the total two-component intermediate composition volume consisting of a renewable paraffinic gasoline component, wherein at least 99 vol-% of said renewable paraffinic gasoline component consists of renewable C4-C12 alkanes selected from renewable n-alkanes, renewable iso-alkanes and renewable cyclo-alkanes, and the ratio of the amount of the renewable C8 n-alkanes to the amount of renewable C8 i-alkanes is from 1 :10 to 1 :2.
  • prenol as a blend component with renewable paraffinic gasoline component are good energy density, modest water solubility and low vapour pressure.
  • Said two-component intermediate composition may be used for further blending, wherein said two-component intermediate composition is used in a gasoline fuel in an amount from 10 to 50 vol-% of the total gasoline fuel volume.
  • a gasoline fuel comprises from 0.5 to 10 vol-% of prenol.
  • prenol a level of prenol.
  • the said gasoline fuel fulfils requirements set in Directive 2009/30/EC, and optionally in EN228:2012 amended 2017.
  • the gasoline fuel comprises from 8 to 49 vol-% of the renewable paraffinic gasoline component.
  • This component alone can provide a significant bio-content for said gasoline fuel.
  • further components of said gasoline fuel may also be at least in part renewable, the use according to this embodiment aids at reducing the fossil content in the gasoline fuel.
  • Gasoline fuels may be obtained when the two-component intermediate composition as described herein, is blended with at least one further component selected from butane and at least one octane enhancer.
  • a process for producing a two-component intermediate composition for gasoline comprising a. providing a glyceride containing feedstock; b. subjecting said feedstock to hydrodeoxygenation and hydroisomerization to obtain a paraffinic product; c. fractionating said paraffinic product and recovering a hydrotreated renewable paraffinic gasoline component consisting of renewable C4- C12 alkanes selected from renewable n-alkanes, renewable iso-alkanes and renewable cyclo-alkanes, preferably a combination of n-alkanes and iso-alkanes; d.
  • the hydrotreated renewable paraffinic gasoline component refers to fraction, obtainable by fractional distillation, comprising hydrocarbons boiling in the gasoline range.
  • said renewable paraffinic gasoline component is derived from renewable sources, such as biological fats or oils by hydrotreating or by Fischer-Tropsch reaction from renewable synthesis gas.
  • hydrocarbon composition Characterizing a hydrocarbon composition by hydrocarbon type [paraffinic (alkanes), naphthenic (cyclo-alkanes), olefinic (alkenes) and aromatic] and carbon number, they may be measured according to ENIS022854 or by other gas chromatography-based detailed hydrocarbon analysis. Using the analysis results, the hydrocarbon composition of the blends was calculated by accounting the blending volumetric ratios.
  • the renewable paraffinic gasoline component has at least some of the following characteristics: melting point ⁇ - 60°C (EEC A1/A2), initial boiling point and boiling range > 40 - 170°C (EN ISO 3405), flash point ⁇ 0°C (EEC A9).
  • melting point ⁇ - 60°C EEC A1/A2
  • initial boiling point and boiling range > 40 - 170°C EN ISO 3405
  • flash point ⁇ 0°C EEC A9
  • hydrotreating refers to hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodehalogenation (such as hydrodechlorination), hydrogenation of double bonds, hydrocracking, hydroisomerization and it also removes some metals. Hydrotreating is needed for removal of covalently bound oxygen from the fatty acid and eventual fatty acid esters, such as reminder glyceride molecules. Typically, this means deoxygenation by hydrogenation i.e. hydrodeoxygenation (HDO) and hydrogenation of double bonds, followed by hydroisomerization.
  • HDO hydrodeoxygenation
  • the hydrodeoxygenation may take place at reaction conditions comprising a temperature in the range from 100 to 500 °C, preferably from 250 to 400 °C, more preferably from 280 - 350 °C, most preferably at temperature of 300-330 °C.
  • the hydrodeoxygenation may take place at reaction conditions comprising a pressure in the range from 0.1 to 20 MPa, preferably from 0.2 to 8 MPa.
  • the weight hourly space velocity (WHSV) in the hydrodeoxygenation reaction a is in the range from 0.5 to 3.0 IT 1 , more preferably from 1.0 to 2.5 IT 1 , most preferably from 1 .0 to 2.0 h 1 .
  • hte flow is in the range from 350 to 900 nl H2/I feed, more preferably from 350 to 750, most preferably from 350 to 500, wherein nl H2/I means normal liters of hydrogen per liter of the feed into the HDO reactor, in the presence of a hydrodeoxygenation catalyst.
  • the hydrodeoxygenation catalyst is preferably selected from Pd, Pt, Ni, Co, Mo, Ru, Rh, W,or any combination of these, such as C0M0, NiMo, NiW, CoNiMo on a support, wherein the support is preferably alumina and/or silica.
  • Hydrotreating may comprise hydrodeoxygenation and hydroisomerization, simultaneously or in sequence. When conducted in sequence, hydrotreating comprises first hydrodeoxygenation and then hydroisomerization.
  • the hydroisomerization step is preferably performed at a temperature from 250 to 400 °C, more preferably from 280 to 370 °C, most preferably from 300 to 350 °C.
  • the hydroisomerization may take place at reaction conditions comprising a pressure, which preferably is from 1 to 6 MPa, more preferably from 2 to 5 MPa, most preferably from 2.5 to 4.5 MPa.
  • the hydrodeoxygenation may take place at reaction conditions comprising a WHSV preferably from 0.5 to 3 h 1 , more preferably from 0.5 to 2 h 1 , most preferably from 0.5 to 1 h 1 , and H2 flow as in-liter H2/liter feed, preferably from 100 to 800, more preferably from 200 to 650, most preferably from 350 to 500.
  • a WHSV preferably from 0.5 to 3 h 1 , more preferably from 0.5 to 2 h 1 , most preferably from 0.5 to 1 h 1
  • H2 flow as in-liter H2/liter feed preferably from 100 to 800, more preferably from 200 to 650, most preferably from 350 to 500.
  • the isomerization treatment is a step which predominantly serves to isomerize at least part of the hydrodeoxygenated raw material. That is, while most thermal or catalytic conversions (such as HDO) result in a minor degree of isomerization (usually less than 5 wt-%), the isomerization step leads to a significant increase in the content of i-paraffins.
  • renewable diesel and renewable paraffinic gasoline components Due to cracking during isomerization, renewable diesel and renewable paraffinic gasoline components are formed.
  • the renewable paraffinic gasoline component thus obtained has typically inadequate octane numbers, and is a challenging component unless blended with further component to form a two-component intermediate composition and/or yet further components to form a gasoline fuel.
  • Hydroisomerization can be carried out in a conventional hydroisomerization unit. Hydrogen is added into the hydroisomerization step. Both the hydrodeoxygenation step and hydroisomerization step may be conducted in the same reactor, and even in the same reactor bed.
  • the hydroisomerization catalyst may be a noble metal bifunctional catalyst such as a Pt containing commercial catalyst, for example Pt- SAPO or Pt-ZSM-catalyst or for example a non-noble catalystsuch as NiW.
  • hydroisomerization is conducted in the presence of an hydroisomerization catalyst containing a support, a metal and a further catalyst material, said support selected from AI2O3 and S1O2, and said metal selected from Pt and Pd and Ni, and said further catalyst material selected from SAPO-11 and SAPO-41 and ZSM-22 or ZSM-23.
  • an hydroisomerization catalyst containing a support, a metal and a further catalyst material, said support selected from AI2O3 and S1O2, and said metal selected from Pt and Pd and Ni, and said further catalyst material selected from SAPO-11 and SAPO-41 and ZSM-22 or ZSM-23.
  • the hydrodeoxygenation and hydroisomerization steps may be performed in the same catalyst bed using e.g. the NiW catalyst in both the hydrodeoxygenation and isomerization.
  • an end product such as gasoline fuel, in particular high octane gasoline fuel
  • a blend is prepared wherein the two-component intermediate composition according to the present disclosure forms part of the end product together with further components, such as octane enhancers.
  • octane enhancers is herein referred to octane improvers such as oxygenates (e.g. ethers and alcohols) and aromatic amines.
  • oxygenates e.g. ethers and alcohols
  • aromatic amines Preferably octane enhancers are not based on metals. They are typically used as minor components in relation to the total volume of the end product.
  • the nature of octane enhancers as additives can be understood by the proportions of the components. For example, N-methyl aniline (NMA), an aromatic amine, is used at a relatively high proportion (1 .5 to 2 % volume additive / volume end product) for desired effect on octane number of the end product.
  • NMA N-methyl aniline
  • an aromatic amine is used at a relatively high proportion (1 .5 to 2 % volume additive / volume end product for desired effect on octane number of the end product.
  • Oxygenates may be used at even higher proportions, from 3 % up to the maximum oxygen and/or oxygenate content permitted by the relevant fuel specification.
  • the amount of an octane enhancer added thereto is typically from 0.5 to 10 vol-% of the gasoline fuel volume as the end product volume.
  • Blending the renewable paraffinic gasoline component and prenol together by volume, to form the two-component intermediate composition of the present disclosure lies within basic skills in the field.
  • a man skilled in the art has different options for blending the two-component intermediate composition with further components to obtain desired grade end products.
  • the order of addition of different components is not crucial for the end product.
  • the renewable paraffinic gasoline component and the second gasoline component are first combined together to form the two-component intermediate composition of the present disclosure, and then further components added thereto.
  • the two-component intermediate composition as defined here contributes to the properties of said end products even if the order of addition varies, hence if the renewable paraffinic gasoline component is initially blended, e.g.
  • ethanol may be blended at a distribution terminal, whereby hygroscopic nature of ethanol can better be taken into account.
  • the gasoline fuel as the end product may, in addition to the two-component intermediate composition, further comprise one or more further hydrocarbon component(s) selected from reformate, alkylate, isomerate and naphtha, which may be of fossil or renewable origin.
  • a man skilled in the art is well aware that in order to meet certain requirements, e.g. butane, i/n- hexane, i/n-pentane, toluene or iso-octane addition may be needed to adjust the gasoline properties.
  • a gasoline fuel is provided when the two- component intermediate composition of the present disclosure is blended with at least one further component selected from butane and octane enhancer(s), such as ethers or alcohols.
  • the octane enhancers may be selected from ETBE, MTBE, TAME, TAEE, mixed ethers, ethanol, methanol, i- or n-propanol, i- or n-butanol, tertiary butanol, or mixed C1 to C5 alkyl alcohols, or any combination thereof. Blending of further component(s) to said two-component intermediate composition provides means for adjusting gasoline fuel characteristics to correspond to desired specifications.
  • said two-component intermediate composition together with at least one further component provides a gasoline fuel fulfilling requirements set in e.g. EN 228:2012, Amended 2017.
  • said further component is selected from octane enhancers.
  • Such gasoline fuel is then compatible with existing motors and at the same time provides a significant part of the energy content therein derived from biological sources, or in other words the bio-component content, contributing to meeting regulations related to use of biofuels in road transport.
  • the bio-component content of the gasoline fuel may be even higher.
  • the gasoline fuel comprising the two- component intermediate composition of the present disclosure has RON as measured according to ASTM D2699 is from 90 to 110, preferably from 95 to 100.
  • the blend RON and MON ratings of a renewable paraffinic gasoline component were studied, and surprisingly the renewable paraffinic gasoline component, wherein at least 99 vol-% of said renewable paraffinic gasoline component consists of renewable C4-C12 alkanes selected from renewable n- alkanes, renewable iso-alkanes and renewable cyclo-alkanes, and the ratio of the amount of the renewable C8 n-alkanes to the amount of renewable C8 i-alkanes is from 1 :10 to 1 :2, improved the aforementioned properties of prenol in two- component intermediate compositions.
  • Another highly paraffinic fossil gasoline component obtained by alkylation process from crude oil, provided opposite results not providing improvement to blend octane ratings.
  • Prenol was blended with three paraffinic components, Paraffinic component 1 according to the present invention and Paraffinic components 2 and 3 as references, to form different two-component intermediates or blends.
  • Tables 2-4 give characterization of said Paraffinic components 1 , 2 and 3 as to hydrocarbon functionalities and carbon numbers.
  • the measured bRON and bMON ratings for each given two-component intermediate composition of prenol with either Paraffinic component 1 , Paraffinic component 2 or Paraffinic component 3, which is a mixture (1 :1 volumetric) thereof, are compiled to Tables 5-6.
  • Table 1 provides the RON and MON measured for neat hydrocarbon components before blending them with prenol. Measurements were conducted according to ASTM D2699.
  • Paraffinic component 1 which is a renewable paraffinic gasoline component as defined in this disclosure, could be characterized as highly paraffinic. However, the i-paraffin content of this component was relatively lower and n-paraffin content higher than in the reference components. Further, the i-paraffin distribution as per carbon numbers was more even especially from C5 to C8.
  • the Paraffinic component 1 was obtained from renewable raw material through hydrodeoxygenation, hydroisomerization and fractionation.
  • the hydrocarbon composition of the Paraffinic component 2 which could also be referred to as a “fossil paraffinic reference gasoline component”, used in these experiments is characterized by its high i-paraffinic content.
  • the hydrocarbon composition as per carbon numbers and hydrocarbon character is compiled in table 3.
  • the most striking property as to carbon numbers and hydrocarbon type, is the high relative amount of C8 i-paraffins. Table 3. Hydrocarbon characterization and carbon number distribution of the
  • Paraffinic component 3 a mixture (1:1 volumetrically) of the Paraffinic component 1 and Paraffinic component 2 was included in the experiments, analyzed correspondingly and the results given in table 4. Table 4. Hydrocarbon characterization and carbon number distribution of the mixture of the previous two, referred to as Paraffinic component 3.
  • blending RON and MON ratings (denoted as bRON and bMON) were calculated for the two-component blends using the formula 1.
  • bRON and bMON RON and MON ratings
  • formula 1 ’’paraffinic component” refers to the hydrocarbon component (here either Paraffinic component 1, Paraffinic component 2 or Paraffinic component 3) and “x” refers to the vol-%/100 of the respective component, paraffinic component or prenol.
  • bMON is calculated respectively.
  • the impact of prenol's blend octanes decreased in relation with increasing prenol volume i.e. the effective octane boost was lower with higher prenol volumes.
  • the bMON ratings were 74.4, 75.4 and 74.4, respectively, as presented in Table 2.
  • ARON * is the RON difference of the neat paraffinic component and the prenol blends presented in this table.
  • octane enhancer ethanol
  • ethanol octane enhancer
  • two-component intermediate compositions comprising prenol and a renewable paraffinic gasoline component were prepared with varying prenol contents, namely 15, 10 and 5 vol-%.
  • Corresponding blends with the same renewable paraffinic gasoline component with ethanol as comparative examples were prepared with corresponding ethanol contents, 15, 10 and 5 vol-%.
  • DVPE for each blend was measured with EN 13016-1 method (at 37.8 °C) according to standard EN228. The comparison of different ethanol and prenol contents with a renewable paraffinic gasoline component is given in figure 3.
  • the same base gasoline was used for both alcohols and for all blend ratios.
  • the DVPE for said neat Paraffinic component 1 was about 39.7 kPa.
  • prenol lowered the vapor pressure (about 37.5, 36.8 and 36.5kPa respectively), whereas ethanol raised it (about 47.8, 48.2 and 48.0 kPa respectively).
  • prenol blends are believed to be attributed to the lower DVPE of prenol itself as well as its longer carbon chain length, which makes it more soluble in hydrocarbons.
  • Lower DVPEs of the two-component intermediate compositions according to the present invention could allow greater use of butane in gasoline fuels.
  • solubility to water is lower with prenol than with ethanol.

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Abstract

L'invention concerne une nouvelle composition intermédiaire à deux composants à indice d'octane renforcé pour essence, comprenant du prénol, et le reste du volume total de la composition intermédiaire consistant en un constituant paraffinique renouvelable de l'essence. L'invention divulgue en outre un procédé pour sa production et son utilisation. La composition intermédiaire à deux composants pour essence comprend du prénol en une quantité de 5 à 20 % en volume par rapport au volume total de la composition intermédiaire à deux composants. Ladite composition intermédiaire à deux composants pour essence a montré expérimentalement des propriétés antidétonantes meilleures que ce qui était prévu.
PCT/FI2022/050322 2021-05-20 2022-05-13 Composition intermédiaire à deux composants à indice d'octane renforcé WO2022243599A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4244704A (en) 1980-01-04 1981-01-13 Texaco Inc. Gasoline composition
FI100248B (fi) 1996-02-05 1997-10-31 Fortum Oil Oy Keskitisleen valmistus
EP1741768A1 (fr) 2005-07-04 2007-01-10 Neste Oil OYJ Procédé pour la production d'hydrocarbures dans l'intervalle des Diesels
US10899988B1 (en) 2018-06-14 2021-01-26 National Technology & Engineering Solutions Of Sandia, Llc Octane hyperboosting in fuel blends

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4244704A (en) 1980-01-04 1981-01-13 Texaco Inc. Gasoline composition
FI100248B (fi) 1996-02-05 1997-10-31 Fortum Oil Oy Keskitisleen valmistus
EP1741768A1 (fr) 2005-07-04 2007-01-10 Neste Oil OYJ Procédé pour la production d'hydrocarbures dans l'intervalle des Diesels
US10899988B1 (en) 2018-06-14 2021-01-26 National Technology & Engineering Solutions Of Sandia, Llc Octane hyperboosting in fuel blends

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BOOT ET AL.: "studied different organic octane enhancers in Progress", ENERGY AND COMBUSTION SCIENCE, vol. 60, 2017, pages 1 - 25

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