WO2018069137A1 - Alkylate gasoline composition with renewable naphtha and iso-octane - Google Patents
Alkylate gasoline composition with renewable naphtha and iso-octane Download PDFInfo
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- WO2018069137A1 WO2018069137A1 PCT/EP2017/075327 EP2017075327W WO2018069137A1 WO 2018069137 A1 WO2018069137 A1 WO 2018069137A1 EP 2017075327 W EP2017075327 W EP 2017075327W WO 2018069137 A1 WO2018069137 A1 WO 2018069137A1
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
- C07C9/16—Branched-chain hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
- C07C9/16—Branched-chain hydrocarbons
- C07C9/21—2, 2, 4-Trimethylpentane
-
- 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
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
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- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/0415—Light distillates, e.g. LPG, naphtha
- C10L2200/0423—Gasoline
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- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
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- 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
- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
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- 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
- C10L2270/00—Specifically adapted fuels
- C10L2270/08—Specifically adapted fuels for small applications, such as tools, lamp oil, welding
-
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/24—Mixing, stirring of fuel components
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- Alkylate gasoline composition with renewable naphtha and iso-octane Technical Field
- the present invention relates to the field of small engine gasoline such as alkylate gasoline, in particular processes for preparing gasoline compositions and gasoline compositions for small utility engines, as well as uses of such gasoline compositions in a spark ignition engine, and uses of a renewable naphtha distillate as a renewable component in a small engine gasoline.
- Small utility engines are used in various portable gasoline powered tools, such as chainsaws and lawnmowers. These engines run on gasoline (otherwise also known as petrol outside the United States), such as normal unleaded 95 octane (RON) gasoline that can typically be obtained from a gas station. These small utility engines are typically 2- or 4-stroke spark ignition engines. Due to the fact that these small utility engines are usually being used in portable gasoline powered tools, it is not feasible to manufacture these engines to be as emission efficient as e.g. car-engines both from an economical viewpoint, but also from a weight and complexity viewpoint. As a consequence thereof, portable gasoline powered tools running on normal unleaded 95 octane (RON) gasoline typically emit significantly more hydrocarbons compared to a modern (e.g.
- Small engine gasoline has been developed to have a mild odour and low emission levels compared to normal unleaded 95 octane (RON) gasoline from the gas station, in that small engine gasoline primarily comprises paraffins and contains no or very little aromatic compounds, such as benzene, as well as very little, but usually no oxygenates such as ethanol. It also contains little or no naphthenes and olefins. Seeing that small engine gasoline is mainly comprised of paraffins, it has a mild odour, and burns more cleanly, producing less particular emissions and fewer deposits. Furthermore the lack of oxygenates, in particular the lack of ethanol helps keep the small utility engine running cleaner for a longer time.
- RON normal unleaded 95 octane
- ethanol absorbs moisture, and if the portable gasoline powered tool is stored for lengthy periods, such as a lawnmower during winter, the ethanol absorbs moisture and may cause corrosion. If the water ethanol mixture separates from the hydrocarbons, octane numbers may become unacceptable.
- Small engine gasoline keeps the emissions low and improves the storage stability thereby providing an improved fuel for small utility engines compared to normal unleaded 95 octane (RON) gasoline.
- RON octane
- small engine gasoline is obtained from fossil origin, as this is currently the economically most feasible.
- the present invention was made in view of the prior art described above, and the object of the present invention is to provide small engine gasoline fulfilling specifications to be used as a small engine gasoline with a more "green” content, and without containing oxygenates, such as ethanol and MTBE, which are challenging components regarding engine operability, emissions and storage.
- oxygenates such as ethanol and MTBE
- the present invention provides a process for preparing a gasoline composition, which comprises (a) admixing with an alkylate base gasoline, such as a fossil alkylate base gasoline, comprising: 90 vol-% or more C 5 - Ci 2 paraffins, 5 vol-% or less of naphthenes, 1 vol-% or less of aromatics, 1 vol-% or less of oxygenates, RON of at least 87, the alkylate base fuel in an amount in the range from 40 to 90 vol% based on the total gasoline composition; (b) a renewable naphtha distillate comprising: 90 vol-% or more C5-C 12 paraffins, 30 vol-% or more C5-C6 paraffins, 5 vol-% or less of naphthenes, 1 vol-% or less of aromatics, 1 vol-% or less of oxygenates, the renewable naphtha distillate in an amount of 1 vol-% or more, such as 3 vol-% or more, such as 5 vol-% or more, e.g.
- a renewable naphtha distillate having a low octane number of around 35-50 (RON) can be mixed with a fossil alkylate base gasoline and still maintain the octane number (RON) provided that / ' so-octane and/or one or more /so-paraffins having an octane number (RON) of at least 95 is admixed.
- the one or more / ' so-paraffins having an octane number (RON) of at least 95 may be selected from C6-C12 /so-paraffins, such as from the list consisting of: 2,3-dimethylbutane, / ' so-octane, 2,2,4-trimethylpentane, 2,3,3-trimethylpentane, 2,2,3-trimethylpentane, 2,2,3-trimethylbutane.
- the one or more C6-C12 /so-paraffins may be /so-octane.
- the process may also further involve adding (d) one or more C 4 - C 5 paraffins in an amount of 10 vol-% or more, such as between 10 - 35 vol-%, where the C 4 - C 5 paraffins are selected from the list consisting of: /so-pentane, / ' so-butane, n-butane, neo-pentane.
- the one or more C 4 - C 5 paraffins may be / ' so-pentane.
- a renewable naphtha distillate typically having a low octane number of around 35-50 (RON) and a low vapour pressure of between 15-25 kPa can be mixed with a fossil alkylate base gasoline and still maintain important parameters such as the research octane number (RON) and motor octane number (MON) as well as the vapour pressure by admixing / ' so-octane and/or one or more / ' so-paraffins having an octane number (RON) of at least 95 together with iso-pentane and/or one or more C 4 - C 5 paraffins.
- the renewable naphtha distillate may comprise an iso-paraffin / n-paraffin ratio of more than 1 , such as more than 1 .2.
- the renewable naphtha distillate may have a RON from 35 to 70, such as from 35 to 60 or from 35 to 50.
- a gasoline composition obtainable according to the process is provided.
- a gasoline composition for a small utility engine comprises (a) a fossil alkylate base gasoline in an amount in the range from 40 to 90 vol% based on the total gasoline composition comprising: 90 vol-% or more C5-C12 paraffins; (b) a renewable naphtha distillate in an amount in the range from 1 to 10 vol% based on the total gasoline composition comprising: 90 vol-% or more C5-C12 paraffins, 30 vol-% or more C5-C6 paraffins; and (c) one or more C6-C12 iso-paraffins in an amount in the range from 10 to 30 vol% based on the total gasoline composition, having a RON of at least 95; wherein the gasoline composition comprises: 90 vol-% or more C5-C12 paraffins, 1 vol-% or less of naphthenes, 1 vol-% or less of aromatics, 1 vol-% or less of oxygenates, RON of at least 92, such as at least 93.
- the one or more C6-C12 iso-paraffins may be selected from the list consisting of: 2,3-dimethylbutane, iso-octane, 2,2,4-trimethylpentane, 2,3,3-trimethylpentane, 2,2,3-trimethylpentane, 2,2,3-trimethylbutane, and the one or more C6-C12 iso-paraffins may be iso-octane.
- the gasoline composition may further comprise: (d) one or more C 4 - C 5 paraffins in an amount of 10 - 35 vol-%, where the C 4 - C 5 paraffins are selected from the list consisting of: iso-pentane, iso-butane, n-butane, neo-pentane.
- the one or more C 4 -C 5 iso-paraffins may be / ' so-pentane.
- the use of the gasoline composition obtainable according to the processes of the invention or the gasoline composition according to the invention in a spark ignition engine is provided.
- the spark ignition engine may be a 2-stroke engine or a 4-stroke engine.
- the spark ignition engine may be part of a portable gasoline powered tool.
- the spark ignition engine may be selected from the list consisting of engines for a: garden tool, forestry tool, chain saw, clearing saw, outboard motor, lawn mower, lawn tractor, string trimmer, snowblower, snowmobile, backpack blower or sucker, water ski, jet ski, motocross, concrete mixers, generators, or the like.
- a renewable naphtha distillate as a renewable component in a small engine gasoline comprising a major portion of a small engine gasoline, which may be of fossil origin, and a minor portion of a renewable naphtha distillate, and where the renewable naphtha distillate comprises: 90 vol-% or more C5-C12 paraffins, 30 vol-% or more C5-C6 paraffins, 5 vol-% or less of naphthenes, 1 vol-% or less of aromatics, 1 vol-% or less of oxygenates.
- the renewable naphtha distillate may have a boiling point range of 30-200 °C, such as 90-200 °C, or 40-180 °C.
- the portion of the renewable naphtha distillate may be in an amount of 1 vol-% or more, 3 vol-% or more, preferably 5 vol-% or more based on the total gasoline composition.
- One of the objects of the present invention is to provide small engine gasoline fulfilling specifications to be used as a small engine gasoline with a more "green” content, and without containing oxygenates, such as ethanol and MTBE, which are challenging components regarding engine operability, emissions and storage.
- the present invention provides a process for preparing a gasoline composition, in particular an alkylate gasoline composition, which comprises (a) admixing with an alkylate base gasoline, (b) a renewable naphtha distillate and (c) one or more C6-C12 iso-paraffins having a RON of at least 95.
- a renewable naphtha distillate typically having a low octane number of around 35-50 (RON) can be mixed with a fossil alkylate base gasoline and still maintain the octane number (RON) provided that / ' so-octane and/or one or more /so-paraffins having an octane number (RON) of at least 95 is admixed.
- Alkylate base gasoline is paraffinic with very little naphthenes, aromatics and oxygenates. It may be derived from the refining of crude oil, where it is typically blended from several petroleum refinery process streams, such as direct distillation of crude oil, catalytic and thermal cracking, hydrocracking, catalytic reforming, alkylation and polymerisation. As a result thereof alkylate base gasoline comprise many different compounds, such as more than 40 or 50 different compounds. For example it may comprise between 40 and 100 different compounds, such as between 40 and 80 different compounds. It may have an initial boiling point (IBP) of about 30 °C or about 35 °C and a final boiling point (FBP) of about 200 °C or about 205 °C.
- IBP initial boiling point
- FBP final boiling point
- the gasoline compositions may have an initial boiling point (IBP) within about 30 °C or within about 35 °C and a final boiling point (FBP) of within about 200 °C or within about 205 °C, for example within 30-205 °C.
- IBP initial boiling point
- FBP final boiling point
- the hydrocarbons present in that distillation range usually range from those containing 4 or 5 carbon atoms to those containing 10 or 1 1 or 12 carbon atoms.
- Alkylate base gasoline is mainly comprised of paraffins (alkanes), which can be straight-chain n-paraffins or the branched iso-paraffins.
- Alkylate base gasoline may have 90 vol-% or more C5-C12 paraffins, such as 95 vol-% or more C5-C12 paraffins, or 98 vol-% or more C5-C12 paraffins.
- the alkylate base fuel may be a fossil alkylate base gasoline or the major part of the alkylate base fuel may be of fossil origin.
- the alkylate base gasoline also has a very low content of naphthenes (cycloalkanes), which are alkanes with at least one non-aromatic ring structure, where the ring typically has 5 or 6 carbon atoms.
- Alkylate base gasoline may have 5 vol-% or less of naphthenes, such as 1 vol-% or less of naphthenes or 0.5 vol-% or less of naphthenes.
- the alkylate base gasoline also has a very low content of aromatics.
- Aromatic compounds contain a benzene ring or other ring structure that is aromatic.
- Alkylate base gasoline may have 1 vol-% or less of aromatics, such as 0.5 vol-% or less of aromatics, or 0.1 vol-% or less of aromatics.
- the alkylate base gasoline also has a very low content of oxygenates.
- Oxygenates are organic molecules that contain oxygen as part of their chemical structure, and are usually employed as gasoline additives to reduce carbon oxides and soot created during the burning of the fuel. Commonly oxygenates comprise alcohols, ethers and esters.
- Alkylate base gasoline may have 1 vol-% or less of oxygenates such as 0.5 vol-% or less of oxygenates, or 0.1 vol-% or less of oxygenates. Usually alkylate base gasolines have no oxygenates at all.
- the alkylate base gasoline may have a Research Octane Number (RON) of at least 87, such as at least 90.
- Premium octane alkylate gasolines may have a higher octane number (RON) of 92 or more, such as above 92 are desirable, for example 93 or more, such as above 93 (RON).
- the higher octane number can help when engines are running hotter than they should, as elevated engine temperatures require higher octane gasoline to prevent pre-ignition, which is to be avoided in small engines.
- the higher octane number is also desirable when using the alkylate gasoline for more demanding tasks, such as in outboard motors, snow mobiles, water skis, jet skis, motocross, and the like.
- the alkylate gasoline is in some countries limited to a maximum 98 octane (RON) by law, such as a maximum of 95 octane (RON).
- Octane numbers measured are not an absolute number, but rather it is relative to a mixture of n-heptane having an octane number (RON and MON) of 0 by definition and 2,2,4-trimethyl pentane having an octane number (RON and MON) of 100 by definition.
- the RON number correlates with full-scale spark-ignited engine antiknock performance at low speed.
- the motor method octane number (MON) correlates with full-scale spark-ignited engine antiknock performance at high speed.
- RON Research Octane Numbers
- MON Motor Octane Numbers
- MON Motor Octane Numbers
- the alkylate base gasoline may have a Motor Octane Number (MON) of at least 80 or 85.
- Premium octane alkylate gasolines may have a higher octane number (MON) of 90 or more, such as above 90.
- Vapour pressure of the gasoline is also a matter of importance relating to in particular engines with a carburettor, which is often present in small engines. While vapour pressure is often manipulated seasonally (higher vapour pressure for winter gasoline, and lower vapour pressure for summer gasoline), there is nevertheless a minimum vapour pressure for gasoline.
- the high vapour pressure of gasoline helps ensuring that the gasoline is in gaseous form in the combustion chamber of the engine.
- the alkylate base gasoline may have a vapour pressure of 50 kPa or more, such as at least 55 kPa or more and as high as 95 kPa.
- the gasoline according to the invention may have a vapour pressure of 50 kPa or more, such as at least 55 kPa or more and as high as 95 kPa.
- the alkylate base fuel may be present as the major amount of the total gasoline composition to be prepared according to the present invention. In particular, it may be in an amount of 40 vol-% or more, such as 45 vol-% or more, or 50 vol-% or more of the total gasoline composition.
- the alkylate base gasoline may equally also be present in a maximum amount of 90 vol-% or less, such as 80 vol-% or less, or 70 vol-% or less, or 60 vol-% or less.
- the alkylate base gasoline may be present in an amount of 40 to 90 vol% based on the total gasoline composition, such as in an amount of 45 to 70 vol% based on the total gasoline composition.
- experiment 1 there is an alkylate gasoline obtained from an alkylation unit and which is then further distilled, and where additional components can be introduced into alkylate gasoline to obtain the specifications given in example 1 , experiment 1 for the alkylate base gasoline.
- the alkylate base gasoline has 90 vol-% or more C5-C12 paraffins (not shown), an aromatics content of 1 vol-% or less, olefin content of 1 vol-% or less, a naphthenes content of 5 vol-% or less (not shown), an oxygenates content of 1 vol-% or less (not shown) and having a vapour pressure above 50 kPa, a RON of at least 92 and a MON at least 90.
- the process for preparing a gasoline composition according to the present invention comprises (a) admixing with an alkylate base gasoline, (b) a renewable naphtha distillate and (c) one or more C6-C12 iso-paraffins having a RON of at least 95.
- a renewable naphtha distillate may be produced as part of the refining of renewable diesel.
- Renewable diesel may be obtained from the processing of fatty acid containing materials, such as animal fats, algae, and plant material.
- Plant material may comprise both vegetable based material, such as vegetable oils as well as oils obtained from other plants, such as oils from trees, e.g. tall oil.
- Renewable diesel and renewable naphtha distillate may be obtained from the hydrotreatment of fatty acids, and derivatives thereof, such as triglycerides.
- the hydrotreatment of fatty acids and derivatives thereof involves deoxygenation reactions, such as hydrodeoxygenation (HDO), and may also involve other hydroprocessing reactions, such as isomerisation (for example hydroisomerisation) and cracking (for example hydrocracking).
- HDO hydrodeoxygenation
- isomerisation for example hydroisomerisation
- cracking for example hydrocracking
- the gasoline compositions may have an initial boiling point (IBP) within about 30 °C or within about 35 °C and a final boiling point (FBP) of within about 200 °C or within about 205 °C, for example within 30-205 "C.
- the hydrocarbons present in that distillation range usually range from those containing 4 or 5 carbon atoms to those containing about 10 or 1 1 or 12 carbon atoms.
- Renewable fuels, such as renewable naphtha distillate are collected from resources, which are naturally replenished on a human timescale, as opposed to fossil fuels, such as petroleum gasoline, which are derived from the refining of crude oil.
- a renewable naphtha distillate may be obtained from the hydrotreatment of fatty acids, and derivatives thereof present in fatty acid containing materials such as animal fats and plant material, the hydrotreatment comprising hydrodeoxygenation and hydroisomerisation, and comprise the fraction with an IBP of 30 °C, such as an IBP of 30 °C or higher and a FBP of 200 °C, such as a FBP of 200 °C or lower.
- the renewable content may also be determined by isotopic distribution involving 14 C, 13 C and/or 12 C as described in ASTM D6866.
- the renewable naphtha distillate is paraffinic with very little naphthenes and virtually no aromatics or oxygenates.
- Renewable naphtha distillate is mainly comprised of paraffins (alkanes), which can be straight-chain n-paraffins or the branched / ' so-paraffins.
- Renewable naphtha may have 90 vol-% or more C5-C12 paraffins, such as 95 vol-% or more C5-C12 paraffins, or 98 vol-% or more C5-C12 paraffins.
- renewable naphtha distillate When the renewable naphtha distillate has been produced as described above as part of the refining of renewable diesel, it may comprise 30 vol-% or more C5-C6 paraffins, such as 40 vol-% or more.
- the renewable naphtha distillate also has a low content of naphthenes (cycloalkanes), which are alkanes with at least one non-aromatic ring structure, where the ring typically has 5 or 6 carbon atoms.
- Renewable naphtha distillate may have 5 vol-% or less of naphthenes, such as 1 vol-% or less of naphthenes or 0.5 vol-% or less of naphthenes.
- the renewable naphtha distillate In addition to mainly comprising paraffins, the renewable naphtha distillate also has a very low content of aromatics. Aromatic compounds contain a benzene ring or other ring structure that is aromatic. Renewable naphtha distillate may have 1 vol-% or less of aromatics, such as 0.5 vol-% or less of aromatics, or 0.1 vol-% or less of aromatics. In addition to mainly comprising paraffins, the renewable naphtha distillate also has a very low content of oxygenates. Oxygenates are organic molecules that contain oxygen as part of their chemical structure, and are usually employed as gasoline additives to reduce carbon oxides and soot created during the burning of the fuel. Commonly oxygenates comprise alcohols, ethers and esters.
- Renewable naphtha distillate may have 1 vol-% or less of oxygenates such as 0.5 vol-% or less of oxygenates, or 0.1 vol-% or less of oxygenates, although it is preferably essentially free of oxygenates.
- experiment 5 there is an example of a renewable naphtha distillate.
- Renewable naphtha distillate may be produced as part of the refining of renewable diesel.
- Such products are commercially available under the tradename Neste renewable naphtha, also known as NexNaphtha, and is produced by Neste Oyj, Finland.
- the below table 1 shows an example of the normalised volume percentages of different hydrocarbons in the renewable naphtha distillate used in example 1 .
- the renewable naphtha distillate may have a RON and/or a MON from 35 to 70, such as from 35 to 60 or from 35 to 50. Some of the renewable naphtha distillates have a RON and/or MON of around 35 to 45, which are too low octane numbers to be useful in small utility engines, which typically requires 87 or higher octane rating ((RON+MON)/2).
- vapour pressure of the gasoline is also a matter of importance in small utility engines.
- the renewable naphtha distillate may have a vapour pressure below 30 kPa, such as below 25 kPa, such as below 20 kPa.
- the vapour pressure of the renewable naphtha may equally also be 10 kPa or higher, such as 15 kPa or higher.
- Such a vapour pressure is too low to be useful in small utility engine, which require a gasoline with a higher vapour pressure, such as 50 kPa or higher, for example 55 kPa or higher.
- the renewable naphtha distillate may be added to mixture in at least 1 vol-% or more based on the total gasoline composition, such as at least 3 vol-% or more or as at least 5 vol-% or more. It is preferred to be able to add as much renewable naphtha distillate as possible in order to increase the "green'Yrenewable part of the gasoline composition according to the present invention. In some cases a maximum of 20 vol-% based on the total gasoline composition is added, for example a maximum of 15 vol-%, such as a maximum of 10 vol-%.
- the one or more iso-paraffins may be mixed in an amount in the range from 10 to 30 vol% based on the total gasoline composition.
- the process for preparing a gasoline composition which comprises (a) admixing with an alkylate base gasoline, (b) a renewable naphtha distillate and (c) one or more C6-C12 iso- paraffins having a RON of at least 95.
- One or more C6-C12 iso-paraffins having a RON of at least 95 is admixed in an amount in the range from 10 to 30 vol% based on the total gasoline composition.
- a renewable naphtha distillate typically having a low octane number of around 35-50 (RON) can be mixed with a fossil alkylate base gasoline and still maintain the octane number (RON) provided that / ' so-octane and/or one or more / ' so-paraffins having an octane number (RON) of at least 95 is admixed.
- the one or more iso-paraffins having an octane number (RON) of at least 95 may be selected from C6-C12 iso-paraffins, such as from the list consisting of: 2,3-dimethylbutane, iso-octane, 2,2,4-trimethylpentane, 2,3,3-trimethylpentane, 2,2,3-trimethylpentane, 2,2,3-trimethylbutane. These iso-paraffins have a RON of at least 95.
- the one or more iso-paraffins having an octane number (RON) of at least 95 may be 2,2,4-trimethylpentane.
- the one or more iso-paraffins having an octane number (RON) of at least 95 may also be iso-octane, which is used to denote one or more of the following three isomers of octane: 2,2,4- trimethylpentane, 2,3,3-trimethylpentane, 2,2,3-trimethylpentane, e.g. 2,2,4- trimethylpentane.
- Iso-octane may be of fossil origin or of renewable origin. It may be prepared synthetically by a number of routes, such as dimerization of iso- butane or iso-butene, e.g. iso-butane and iso-butene obtained from a renewable source.
- a renewable naphtha distillate typically having a low octane number of around 35-50 (RON) and a low vapour pressure of between 15-25 kPa can be mixed with a fossil alkylate base gasoline and still maintain important parameters such as the research octane number (RON) and motor octane number (MON) as well as the vapour pressure by admixing / ' so-octane and/or one or more /so-paraffins having an octane number (RON) of at least 95 together with iso-pentane and/or one or more C 4 - C 5 paraffins.
- the process of the present invention may also involve further adding (d) one or more C 4 - C 5 paraffins in an amount of 10 vol-% or more, such as between 10 - 35 vol-%, where the C 4 - C 5 paraffins are selected from the list consisting of: iso-pentane, iso-butane, n-butane, neo-pentane.
- the one or more C 4 - C 5 paraffins may be /so-pentane.
- Iso-octane may be of fossil origin or of renewable origin.
- the renewable naphtha distillate may be produced as part of the refining of renewable diesel, and as such has undergone hydrotreatment comprising hydrodeoxygenation and hydroisomerisation.
- the renewable naphtha distillate may comprise an iso-paraffin / n-paraffin ratio of more than 1 , such as more than 1 .2.
- the ratio may be between 1 and 2.
- the content of the renewable naphtha distillate may advantageously be isomerised beyond its initial isomerisation ratio to yield an iso-paraffin / n-paraffin ratio of above 2, such as 5, 8, 10, 15, 20, 30 or above.
- the isomerisation isomerises both the n-pentane and the n-hexane content of the naphtha distillate, and as such it prepares iso-pentane, and removes n-hexane as iso-hexane. Further isomerising the renewable naphtha distillate does not result in a loss of product, as would be the case with a more narrow distillation or with cracking, or if n-paraffins had been removed using molecular sieves.
- the process for preparing a gasoline composition according to the present invention which comprises (a) admixing with an alkylate base gasoline, (b) a renewable naphtha distillate and (c) one or more C6-C12 iso-paraffins having a RON of at least 95, and optionally (d) one or more C 4 - C 5 paraffins.
- a gasoline composition obtainable according to the process is provided, as well as a gasoline composition for a small utility engine comprising is provided.
- the gasoline composition comprising (a) a fossil alkylate base gasoline in an amount in the range from 40 to 90 vol% based on the total gasoline composition comprising: 90 vol-% or more C5-C12 paraffins; (b) a renewable naphtha distillate in an amount in the range from 1 to 10 vol% based on the total gasoline composition comprising: 90 vol-% or more C5-C12 paraffins, 30 vol-% or more C 5 - C6 paraffins; and (c) one or more C6-C12 iso-paraffins in an amount in the range from 10 to 30 vol% based on the total gasoline composition, having a RON of at least 95; wherein the gasoline composition comprises: 90 vol-% or more C5-C12 paraffins, 1 vol-% or less of naphthenes, 1 vol-% or less of aromatics, 1 vol-% or less of oxygenates, RON of at least 92, such as at least 93.
- the one or more C6-C12 iso-paraffins may be selected from the list consisting of: 2,3-dimethylbutane, iso-octane, 2,2,4-trimethylpentane, 2,3,3-trimethylpentane, 2,2,3-trimethylpentane, 2,2,3-trimethylbutane, and the one or more C6-C12 iso-paraffins may be iso-octane.
- the gasoline composition may further comprise: (d) one or more C 4 - C 5 paraffins in an amount of 10 - 35 vol-%, where the C 4 - C 5 paraffins are selected from the list consisting of: iso-pentane, iso-butane, n-butane, neo-pentane.
- the one or more C 4 -C 5 iso-paraffins may be / ' so-pentane.
- the use of the gasoline composition obtainable according to the processes of the invention or the gasoline composition according to the invention in a spark ignition engine is provided.
- the spark ignition engine may be a 2-stroke engine or a 4-stroke engine.
- the spark ignition engine may be part of a portable gasoline powered tool.
- the spark ignition engine may be selected from the list consisting of engines for a: garden tool, forestry tool, chain saw, clearing saw, outboard motor, lawn mower, lawn tractor, string trimmer, snow blower, snowmobile, backpack blower or sucker, water ski, jet ski, motocross, concrete mixers, or generators.
- the spark ignition engine may have a cylinder displacement of 500 cm 3 or less, such as 100 cm 3 or less.
- Chainsaws and other garden or forestry tools may have a cylinder displacement of 100 cm 3 or less.
- the gasoline compositions described herein or obtainable according to the present invention is suitable for small utility engines, in particular to the mentioned items containing a spark ignition engine, as these items are in many cases seasonal items used predominantly during winter or summer, or used infrequently, such as a generator. This is in part because of the absence or very low content of oxygenates in the gasoline compositions. Oxygenates such as ethanol are often added to regular unleaded 95 octane (RON) gasoline to improve the octane number, and bio-ethanol added to such gasoline also increases the renewable content of gasoline, and thereby the "green" profile of a fossil gasoline product. However, ethanol absorbs moisture over time which may cause corrosion and start trouble after lengthy storage of such items.
- the gasoline compositions may have an initial boiling point (IBP) of about 30 °C or about 35 °C and a final boiling point (FBP) of about 200 °C or about 205 °C, for example from 30-205 °C.
- the gasoline compositions may have an initial boiling point (IBP) within about 30 °C or within about 35 °C and a final boiling point (FBP) of within about 200 °C or within about 205 °C, for example within 30-205 °C.
- a renewable naphtha distillate as a renewable component in a small engine gasoline comprising a major portion of a small engine gasoline, which may be of fossil origin, and a minor portion of a renewable naphtha distillate, and where the renewable naphtha distillate comprises: 90 vol-% or more C5-C12 paraffins, 30 vol-% or more C5-C6 paraffins, 5 vol-% or less of naphthenes, 1 vol-% or less of aromatics, 1 vol-% or less of oxygenates.
- the renewable naphtha distillate may have a boiling point range of 30-200 °C, such as 90-200 °C, or 40-180 °C.
- the boiling point range being expressed as initial boiling point (IBP) and final boiling point (FBP). That is that the boiling point range may be within 30-200°C, such as within 90-200°C or 40-180°C.
- the portion of the renewable naphtha distillate may be in an amount of 1 vol-% or more, 3 vol-% or more, preferably 5 vol-% or more based on the total gasoline composition.
- a number of mixtures of an alkylate base gasoline (a light alkylate distillate of fossil origin obtained from Neste Oyj, Naantali) with one or more of a renewable naphtha distillate (having a composition as shown in table 1 above), iso-pentane, and iso-octane (2,2,4-trimethylpentane) has been prepared as shown in the below table 2.
- the density was measured according to ENISO12185, vapour pressure according to EN13016-1 , DIS-E70 and DIS-E100 according to ENISO3405, the RONc according to ENISO5164, the MONc according to ENISO5163, and aromatics, olefins, n-hexane, benzene, cycloalkanes and paraffins according to ENISO22854.
Abstract
Description
Claims
Priority Applications (11)
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EP17784603.7A EP3526314B1 (en) | 2016-10-13 | 2017-10-05 | Alkylate gasoline composition with renewable naphtha and iso-octane |
SG11201903222PA SG11201903222PA (en) | 2016-10-13 | 2017-10-05 | Alkylate gasoline composition with renewable naphtha and iso-octane |
DK17784603.7T DK3526314T3 (en) | 2016-10-13 | 2017-10-05 | Alkylate gasoline composition with renewable naphtha and isooctane |
MX2019003695A MX2019003695A (en) | 2016-10-13 | 2017-10-05 | Alkylate gasoline composition with renewable naphtha and iso-octane. |
KR1020197009322A KR102229503B1 (en) | 2016-10-13 | 2017-10-05 | Alkylated gasoline composition with renewable naphtha and iso-octane |
JP2019518996A JP6774566B2 (en) | 2016-10-13 | 2017-10-05 | Alchemed gasoline containing renewable naphtha and isooctane |
AU2017343503A AU2017343503B2 (en) | 2016-10-13 | 2017-10-05 | Alkylate gasoline composition with renewable naphtha and iso-octane |
BR112019007510-0A BR112019007510B1 (en) | 2016-10-13 | 2017-10-05 | Composition of alkylated gasoline with renewable naphtha and isoctane |
CN201780062191.6A CN109844073B (en) | 2016-10-13 | 2017-10-05 | Alkylated gasoline composition with renewable naphtha and iso-octane |
CA3038000A CA3038000C (en) | 2016-10-13 | 2017-10-05 | Alkylate gasoline composition with renewable naphtha and iso-octane |
US16/339,901 US10894927B2 (en) | 2016-10-13 | 2017-10-05 | Alkylate gasoline composition with renewable naphtha and iso-octane |
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FI20165785A FI20165785A (en) | 2016-10-13 | 2016-10-13 | Alkylaattibensiinikoostumus |
FI20165785 | 2016-10-13 |
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PCT/EP2017/075327 WO2018069137A1 (en) | 2016-10-13 | 2017-10-05 | Alkylate gasoline composition with renewable naphtha and iso-octane |
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US (1) | US10894927B2 (en) |
EP (1) | EP3526314B1 (en) |
JP (1) | JP6774566B2 (en) |
KR (1) | KR102229503B1 (en) |
CN (1) | CN109844073B (en) |
AU (1) | AU2017343503B2 (en) |
BR (1) | BR112019007510B1 (en) |
CA (1) | CA3038000C (en) |
DK (1) | DK3526314T3 (en) |
FI (1) | FI20165785A (en) |
MX (1) | MX2019003695A (en) |
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EP3526314B1 (en) | 2016-10-13 | 2020-07-22 | Neste Oyj | Alkylate gasoline composition with renewable naphtha and iso-octane |
WO2021099220A1 (en) | 2019-11-21 | 2021-05-27 | Neste Oyj | Gasoline composition with octane synergy |
WO2022017912A1 (en) | 2020-07-20 | 2022-01-27 | Shell Internationale Research Maatschappij B.V. | Fuel composition |
US20230227745A1 (en) * | 2020-08-31 | 2023-07-20 | Neste Oyj | Octane enhanced intermediate hydrocarbon composition |
EP4286496A1 (en) | 2022-06-01 | 2023-12-06 | Haltermann Carless Deutschland GmbH | Small engine fuel composition with specific content of iso-octane |
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MX2019003695A (en) | 2019-06-24 |
BR112019007510A2 (en) | 2019-07-02 |
FI20165785A (en) | 2018-04-14 |
CN109844073A (en) | 2019-06-04 |
JP6774566B2 (en) | 2020-10-28 |
EP3526314A1 (en) | 2019-08-21 |
AU2017343503B2 (en) | 2020-01-23 |
US10894927B2 (en) | 2021-01-19 |
DK3526314T3 (en) | 2020-09-28 |
SG11201903222PA (en) | 2019-05-30 |
AU2017343503A1 (en) | 2019-04-11 |
BR112019007510B1 (en) | 2022-05-10 |
CA3038000C (en) | 2021-07-20 |
JP2019534925A (en) | 2019-12-05 |
CN109844073B (en) | 2021-06-08 |
KR20190041527A (en) | 2019-04-22 |
CA3038000A1 (en) | 2018-04-19 |
EP3526314B1 (en) | 2020-07-22 |
US20200048569A1 (en) | 2020-02-13 |
KR102229503B1 (en) | 2021-03-19 |
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