PL192296B1 - Fuel compositions - Google Patents

Abstract

Unleaded blend compositions, as well as formulated gasolines containing them have a Motor Octane Number (MON) of at least 80 comprising at least 2 % of component (a), which is at least one branched chain alkane of MON value of at least 90 and of boiling point 15-160 DEG C or a substantially aliphatic hydrocarbon refinery stream, of MON value of at least 85, at least 70 % in total of said stream being branched chain alkanes, said stream being obtainable or obtained by distillation from a refinery material as a cut having Initial Boiling Point of at least 15 DEG C and Final Boiling Point of at most 160 DEG C, said Boiling Points being measured according to ASTMD2892, and as component (g) at least 5 % of at least one paraffin, liquid hydrocarbon or mixture thereof e.g. aromatic hydrocarbon compound or olefinic hydrocarbon of bp60-160 DEG C, especially of MON value at least 70 and RON at least 90 or as component (g) at least 20 % of one or more refinery streams. The component (a) gives rise to reduced emissions to the composition or gasoline on combustion.

Description

Description of the invention

The present invention relates to a lead-free composition and the use of the unleaded composition for the production of unleaded gasoline.

For many years, manufacturers of spark ignition engines have tried to increase efficiency in order to optimally use hydrocarbon fuels. However, such engines require high octane gasolines, which have been obtained especially by adding organoleaded substances and more recently in the case of unleaded gasoline by adding MTBE (tertiary butyl methyl ether). However, the combustion of any gasoline leads to the emission of harmful substances such as carbon dioxide, carbon monoxide, nitrogen oxides (NOX) and toxic hydrocarbons, which are undesirable emissions.

The object of the invention is to provide a lead-free composition which is suitable for the production of gasoline with low emissions of harmful substances during its combustion.

According to the invention, a lead-free composition having a motor octane number (MON) of at least 80 is characterized in that it contains at least 10% by volume, based on the total composition, of component (a) (i) being refined aliphatic hydrocarbons with a MON value of at least 85, with at least 70% of the total of this component being branched chain alkanes, which component is a mixture of different refinery fractions, each fraction obtained by distillation from the alkylate as a fraction with an initial boiling point of at least 15 ° C and a final boiling point a boiling point of at most 160 ° C and boiling points as measured by ASTMD2892, and contains as component (g) at least 5% of at least one paraffinic, aromatic or olefinic hydrocarbon having a boiling point of 60-160 ° C, the composition having no more than 5%, based on the total composition, of a hydrocarbon with a boiling point above 160 °, less than 5% 2,2,3-trimethylbutane or 2,2,3-trimethylpentane, and 2-40% by volume aromatics.

Preferably, the lead-free composition comprises 15-65%, especially 20-35% by volume of component (a) (i).

According to the invention, the above-defined unleaded composition is used to prepare a refined unleaded gasoline containing at least one motor gasoline additive. In particular, a lead-free composition is used which contains 15-65%, especially 20-35% by volume of component (a) (i).

All boiling points (i.e.,) quoted herein are for atmospheric pressure.

It was unexpectedly found that the presence of component (a) (i) in unleaded gasoline with a MON number of at least 80, reduces the emission of harmful substances generated during gasoline combustion, in particular when combustion of gasoline containing at least 10% of component (a) (and ) as defined above.

Preferably the lead-free composition comprises 10-70% aliphatic hydrocarbons.

The lead-free composition as defined above contains no more than 5% of the total composition, e.g. less than 3%, even less than 1%, of hydrocarbon with m.p. greater than 160 ° C, especially compounds with at least 2 hydrocarbon rings such as naphthenes.

The content of 2,2,3-trimethylbutane (called triptan) or 2,2,3-trimethylpentane in the composition is preferably less than 4%.

The presence of at least 10% of component (a) (ii), which is at least one branched-chain alkane with a MON number of at least 80, also contributes to reducing the emission of harmful substances during the combustion of unleaded gasoline with a MON number of at least 80. at least 90 and a boiling point in the range 15-160 ° C, especially different from 2,2,3-trimethylbutane and 2,2,3-trimethylpentane.

In particular, the reduction of pollutant emissions takes place when burning unleaded gasoline fuel with a MON value of at least 80, which contains at least 10% of component (a), defined above as (a) (i) and (a) (ii), in a spark ignition engine.

Preferably, a lead-free composition having a MON of at least 80 comprises at least 10% by volume of the total composition (e.g. 10 to 70%) of component (a) which is at least one branched alkane with a MON of at least 90 and a boiling point at the range 15-160 ° C, e.g. 15-100 ° C. The content of alkanes, relative to the total amount of saturated compounds

The concentration of the concentration in the composition is at least 10%, 20% or 30%. Preferably, the alkane content, based on the total amount of saturated compounds in the composition, is 10-50%. This lead-free composition comprises as component (g) at least 5% of at least one paraffinic hydrocarbon, aromatic hydrocarbon or olefinic hydrocarbon, i.e. 60-160 ° C, with no more than 5% of the total composition, e.g. less than 3%, hydrocarbon with m.p. greater than 160 ° C, especially naphthenes, and preferably less than 5%, e.g. less than 4%, of 2,2,3-trimethyl-butane and 2,2,3-trimethylpentane.

A lead-free composition having an Octane Number (MON) of at least 81 or 85 and a Research Octane Number (RON) of at least 91 or 94, preferably comprises:

- at least 15% by volume, based on the total composition, of component (a) consisting of at least one branched chain hydrocarbon which is an alkane of 8-12 carbon atoms with three methyl or ethyl branches (called compound (A)),

- component (g) being at least one liquid hydrocarbon (e.g. paraffinic, aromatic or olefinic hydrocarbon) or a mixture of hydrocarbons as defined in 60-160 ° C and with a MON number of at least 70 and RON of at least 90, the total content of which is at least 20%,

- wherein the content of 2,2,3-trimethylpentane is less than 5%, in particular less than 1%, in particular less than 0.5% and most preferably the total content of 2,2,3-trimethylbutane and 2,2,3- trimethylpentane is less than 0.5%.

Preferably, a lead-free composition having an octane number (MON) of at least 81 or 85 and a RON value of at least 91 or 94, comprises component (a) as defined above, and comprises as component (g) at least 20% refinery-derived hydrocarbons of one or more more refinery streams, especially the components referred to as (b) to (e) hereinafter, such that the lead-free composition contains a total of at least 70% saturated hydrocarbons.

The refinery-derived aliphatic hydrocarbon stream (aliphatic refinery stream) generally comprises at least 90% aliphatic hydrocarbons (e.g., at least 95%). The remainder, preferably up to 5%, may be non-aliphatic hydrocarbons such as cycloaliphatic (e.g. cyclopentane, cyclohexane), linear or branched alkenes (e.g. butenes, pentenes, hexenes, heptenes and octenes) and aromatic hydrocarbons (such as benzene and toluene), with no aromatic hydrocarbons being preferred.

The MON value of said stream is at least 85 (e.g., at least 87, or 90 or 92), especially less than 100 (e.g., 85-96 or 87-95), most preferably 87-90 or 90-95. The RON value of said stream may be 0.5-3.5, especially 1.0-3.5 or 0.5-2.5 units above its MON value, such as RON values of 88-98 or 89.5-96.

In said stream at least 70% in total are branched chain alkanes, wherein one compound or at least two compounds (e.g., 2-10 different compounds) may be present. Preferably, 2-4 different alkanes are present in the stream, each in an amount of at least 10%, especially 20%, e.g. 20-60% in said stream. Thus, the stream may, for example, contain: at least 70% isopentane; or at least 10% (e.g. 10-40%) of each of 2,3-dimethylbutane (e.g. 20-40%), isopentane, 2,3-dimethylpentane (e.g. 2-40%) and 2, 4-dimethylpentane (e.g. 20-40%); or at least 10% (e.g. 10-40%) of each of 2,3-dimethylbutane, 2,3- and 2,4-dimethylpentanes (e.g. 20-40%) and isooctane (e.g. 20-40%) . Streams containing less than 30% isopentane (e.g., 5-25% isopentane) may be preferred, especially if the composition comprises at least 5% tritane or 2,2,3-trimethylpentane. The total branched alkanes content of said stream is at least 70% (e.g. such as 70-85%) with the remainder being any linear alkanes such as n-butane, n-pentane and / or non-aliphatic hydrocarbons indicated above.

Refinery-derived aliphatic hydrocarbons (aliphatic refinery stream) are typically produced from an alkane conversion product, which in turn is produced by reacting one or more alkanes or alkenes (e.g., 3-5 carbon atoms), especially branched compounds. Preferably, an alkane (e.g. isobutane) and alkene (e.g. isobutene) are reacted to form an alkylate. Alkylates are known refining products, see, e.g., Our Industry Petroleum, 2nd Ed. by British Petroleum Co., London, ed. 4, publ. 1970, page 187. Acid catalysts are commonly used in the alkylate production process. These can be soluble catalysts such as protic acids, e.g. hydrogen fluoride or sulfuric and phosphoric acids, or insoluble catalysts such as zeolites or heteropolyacids Mo or W. Alkylates usually have a boiling range of IBP (initial boiling point) of at least 15 ° and FBP (final boiling point) in the range 170-210 ° C. e.g. 175-190 ° C or 185-205 ° C. The refinery stream for use in the compositions of the invention is preferably produced as a fraction from the distillation of said material, e.g.

PL 192 296 B1 by isolating fractions at 15-60 ° C (e.g. 30-60 ° C), 60-80 ° C, 80-90 ° C, 90-95 ° C, 95-100 ° C, 100-103 ° C, 103-106 ° C, 106-110 ° C, 110-115 ° C, 115-125 ° C, 125-140 ° C, or 140-160 ° C; a mixture of different fractions may be used, e.g. 15-60 ° C with at least one of 60-80 ° C, 80-90 ° C, 90-95 ° C and 95-100 ° C, or 60-80 ° C with at least one of 80-90 ° C, 90-95 ° C, 95-100, 100-103 ° C or 103-106 ° C, or a combined fraction, e.g. 80-106 ° C or 90-106 ° C. Preferably, the fraction is an alkylate distilled product in the temperature range 15-160 ° C or 15-140 ° (especially 15-100 ° C or 30-100 ° C or 60-160 ° C), or 60-140 (e.g. 60 ° C). -100 or 90-125 ° C). Fractions with temperatures in the range 15-160 ° C (especially 90-125 ° C or 15-100 ° C, e.g. 60-100 ° C) have been found to yield unleaded gasolines which upon combustion give reduced total hydrocarbon emissions and carbon oxides, e.g. CO2 emissions, compared to emissions from total alkylate or especially from fractions above 160 ° C. The alkylate fraction above 160 ° C can be used as jet fuel, diesel or kerosene, while the alkylate fraction below 160 ° C or below 100 ° C can be used in gasolines. The 60-160 ° C fractions can be used in summer gasoline due to their reduced Reid vapor pressure. Fractions below 100 ° C can also be used to increase the volatility of unleaded gasolines, e.g. to enable the supply of gasolines having an evaporation value at 100 ° C of at least 46%.

Preferably the fraction has a boiling range of at least partially 90-106 ° C, e.g. 90-95 ° C, 95-100 ° C, 100-103 ° C or 103-106 ° C as this gives the optimal octane number in combination with harmful substances emissions. These fractions may be used as such in compositions according to the invention and in gasolines, but may also be mixed with at least one higher bp fraction, in particular 106-100 ° C, 110-115 ° C, 115-125 ° C or 125 ° C. 140 ° C (e.g. 106-125 ° C), preferably in a ratio of 5: 1 to 1:30, or mixed with at least one lower bp fraction, especially 60-80 ° C or 80-90 ° C (e.g. 60-90 ° C), preferably in a ratio of 9: 1 to 1: 9, e.g. 5: 1-1: 1.

Application of the fraction with at least partial t.s. 90-106 ° C as the only or main component (a) in unleaded compositions and gasolines with component (g), provides pure high-octane unleaded gasolines, especially oxygenate-free gasolines with a RON value of at least 97 and a MON value of at least 86, with low emissions harmful substances. Examples of such compositions and gasolines are those with RON 97-99.5 or 97.5-99, MON 86.5-89, RVP 55-65 kPa, e.g. 55-60 kPa, 12-35% evaporation at 70 ° C , 46-62% evaporation at 100 ° C, 95-100% evaporation at 150 ° C, 97.5-100% evaporation at 180 ° C, density 0.715 to 0.74 kg / l, e.g. 0.72-0.738 kg / l, benzene content 0.5-1.5%, e.g. 0.5-1%, aromatics 16-28%, e.g. 16-23%, olefins 3-14%, e.g. 4-12%. They can be made from mixtures of butane 0 or 0.5-6.6%, full range alkylate boiling range 1-25%, e.g. 5-25%, light hydrocracking products 0 or 15-25%, full range steam cracked white spirit 10-45%, kerosene 0 or 0.5-5%, full range catalytically cracked white spirit 0 or 1%, 2,2,4-trimethylpentane 0 or 0.5-25%, e.g. 0.5- 5%, and the alkylate fraction usually in total 25-45%. The latter may be the fraction mentioned above 90-95 ° C, 95-100 ° C, 100-103 ° C, 103-106 ° C, used individually in the amount of 25-45% or a mixture of one or more of these fractions in the amount of 1-40% (in total of the total composition) and 5-40% of the bp 15-60, 60-80 (especially 3-15%) m.p. 106-110, 110-115, 115-125 ° C (especially 7-40%, e.g. 7-20%).

In addition, the remaining fractions, i.e. those above and below the 90-106 ° C fraction, especially the fractions boiling partially in the range of 15-80 ° C and the fractions boiling in the range of 106-125 ° C, can be combined in the proportion of 5: 1 to 1: 5. The use of such combined fractions as component (a) together with component (g) in the composition of the invention and in gasolines can provide clean, octane unleaded gasolines as defined below, especially oxygenate-free gasolines with RON values of at least 92 and MON values. at least 80, and with low emissions of harmful substances. Examples of such compositions and gasolines made from a blend of fractions with high and low t.s. are those with RON 92-98, e.g. 92-95 or 95-98, MON 80-88, e.g. 80-84 or 84-88, RVP 50-65 kPa, e.g. 50-55 or 55-60 kPa, 12-35% evaporation at 70 ° C, 46-62% evaporation at 100 ° C, 94-100% evaporation at 150 ° C, 97.5-100% evaporation at 180 ° C, density 0.715 to 0.74 kg / l, e.g. 0.72-0.738 kg / l, benzene content 0.5-1.5%, e.g. 0.5-1%, aromatics 13-28%, e.g. 13-20%, olefins 3-14 %, e.g. 3-10%. They can be made from mixtures of butane 0 or 0.5-3%, full range alkylate boiling range 10-40%, e.g. 15-30%, full range steam cracked white spirit 15-50%, e.g. 15-35%, kerosene 0 to 10-20% and the alkylate fraction usually in total 25-45%. The latter fraction may be 5-25% (in total based on the total composition) of one or more fractions of m.p. 15-60 ° C, 60-80 ° C and 80-90 ° C, and a total of 10-30% (based on the total composition) of the fraction, i.e. 106-110 ° C, 110-115 ° C and 115-125 ° C, especially 110-125 °.

PL 192 296 B1

In this way, substantially all of the alkylate can be converted to two pure fuel products with higher and lower octane numbers.

A method of producing at least two pure gasoline-suitable compositions comprises fractionating a reaction product containing mostly isoalkanes, e.g. an isomerization or alkylation product, e.g. 15-160 ° C, to produce a first fraction boiling at least partially in the range of 90-106 ° C and a second fraction boiling at a temperature lower than the said first fraction, and a third fraction boiling at a temperature above said first fraction, compiling said first fraction as component (a) with component (g) as defined above to form a first high-octane unleaded gasoline composition having a RON of at least 97 and a MON of at least 86 with low emissions during combustion, and combining said second and third fractions as component (a) with component (g) as defined above to provide at least one second high-octane unleaded gasoline composition with a RON of at least 92 and a MON of at least 80, and with low emissions of harmful substances during combustion. In both cases, these gasolines can be prepared without the need to use high-octane oxygenate.

A method of producing fuels, comprises distilling a reaction product, e.g., an alkylate, to obtain a first fraction above 160 ° C and a second fraction below 160 ° C, and mixing said first fraction with the other components of a liquid hydrocarbon blend to produce a jet fuel, diesel fuel or kerosene, and mixing of said second fraction with the other constituents of the gasoline liquid mixture to produce motor gasoline.

Examples of branched chain alkanes (typically 4-12 carbon atoms, e.g. 4-8 carbon atoms) which constitute component (a) are isoalkanes with 4-8 carbon atoms, especially isobutane, isopentane and isooctane, and dimethylalkanes such as 2,3-dimethylbutane. A branched chain alkane usually has one, preferably two methyl (Me) groups on the second carbon atom in the alkane chain. Branched alkanes typically constitute at least 30%, especially 30-80%, e.g. 50-80%, of the total saturated hydrocarbons in the composition or the total of the saturated hydrocarbons in the alkylate fraction, the rest being essentially other branched chain alkanes not meeting the given definition. e.g. on tw 100-160 ° C or a lower MON value and / or linear hydrocarbons, e.g. 4-8 carbon atoms as defined above. Saturated hydrocarbons may contain small amounts of cycloalkanes as defined above.

The compositions of the invention typically contain less than 5% of tritane or 2,2,3-trimethylpentane, especially less than 4.9% or 1%, and in particular are substantially free of tritane and 2,2,3-trimethylpentane (e.g. less than 0.5% or 0.1% of the sum of both of the above compounds). However, if desired, and especially for fractions boiling above 60 ° C, e.g. 60-160 ° C or 60-100 ° C, triptan and / or 2,2,3-trimethylpentane may be present in an amount of at least 5% or 8%, e.g. 5-20%, of the composition.

Typically, component (g) in the compositions of the invention is at least one paraffinic, aromatic and / or olefinic hydrocarbon, e.g. less than 160 ° C. Examples of the listed components are the components (b) - (f) discussed below, one or two or more of these components may be present.

Component (b) is at least one saturated aliphatic liquid hydrocarbon having 4-12 carbon atoms, especially 4-10, preferably 5-10, e.g. 5-8 carbon atoms. Component (b) which is contained in at least one isomerization product, a full range alkylate having an FBP greater than 170 °, crude gasoline, light reformate, light cracking product and aviation alkylate may also be used.

Preferably, the lead-free composition of the invention comprises at least one olefin (e.g. in an amount of 1-30%, especially 8-18%) and / or at least one aromatic hydrocarbon (e.g. in an amount of 1-50%, especially 3-35%). ) and / or less than 5% benzene. The composition may preferably contain 5-40% of component (a), less than 1% benzene, and may have a Reid vapor pressure at 37.8 ° C as measured by AST-MD323 of 30-120 kPa. The unleaded composition is usually the basic ingredient of unleaded motor gasoline.

Branched chain alkanes, e.g. compounds A, may be alkanes with 8-12 carbon atoms (especially 8-10 or 8 or 10 carbon atoms) with three methyl and / or ethyl branches. Methyl branching is preferred. The compounds usually have the longest carbon chain, called the backbone chain, of 4-6 carbon atoms (especially 4 to 5) to which methyl and / or ethyl branches are attached. Preferably, especially for: first to tenth moieties

As defined below, there are no branching groups other than methyl or ethyl, and there are especially no linear alkyl groups of more than 2 carbons in the carbon backbone, and no 1,2-ethylene or 1,3-propylene groups in the chain. especially methylene groups in the chain, except as part of an ethyl group; thus, especially there are no n-propyl or n-butyl groups forming part of the backbone chain. Preferably, the composition also includes at least one alkane compound (A) of 9-12 carbon atoms (e.g., 9 or 10 carbons), it also includes less than 50% or 10% of an alkane compound (A) of 8 carbon atoms.

The compounds may have 1 or 2 methyl or ethyl groups attached to the same carbon atom of the backbone chain, especially 1 or 2 methyl groups and 0 or 1 ethyl groups. The carbon of the backbone in the backbone is non-terminal, i.e. it is the internal carbon of the backbone, especially the 2nd, 3rd and / or 4th consecutive carbon in the backbone. A geminal compound (having two identical substituents on the same carbon atom) is preferred, especially a compound having geminal methyl substituents on the carbons at the 2, 3 or 4 position, especially at the 2-position, but especially at the 3-position.

In the first moiety of compounds A there are a pair of geminal branching methyl substituents which are in position 2.

In the second moiety of compounds A there is one pair of geminal branching methyl substituents on the 4-6th carbon of the backbone chain. The compounds of the second moiety preferably have a MON value of at least 100.

In the third group of compounds A there is one geminal methyl branch, ie -CMe2- in the backbone, while on one of the adjacent carbon atoms of the backbone there is a methyl or ethyl branch, especially a methyl branch.

In the fourth grouping of compounds A there is one pair of geminal methyl branches at position 2 of the carbon skeleton and there is a methyl branch at position 3 of the carbon skeleton. Such compounds typically have an RON value of at least 111. Preferred compounds have 8 or 10 carbon atoms.

In the fifth moiety of compounds A, there are three methyl or ethyl substituents on different backbone carbon atoms, especially on the vicinal (adjacent) carbon atoms.

The sixth group of compounds A has a linear 4 to 6 carbon backbone and three methyl branches, one pair of which is a geminal group (CMe2), especially in the absence of a 1,2-ethyl group in the backbone.

In the seventh grouping of compounds A there is a linear 5 or 6 carbon skeleton and three branches, one pair of which is one geminal group. The compounds are usually liquid at 25 ° C and generally have an RON value greater than 105. Preferably, only methyl branches are present; such compounds typically have a MON value of at least 101.

In the eighth, preferred moiety of compounds A, these compounds contain one chained carbon atom with geminal methyl branches, one branch on the vicinal carbon to the geminal carbon, and any -C-ethyl chain group having 5 carbon atoms linked to a backbone chain, i.e. they contain a (ethyl) 2CH- or ethyl-CMe2- group.

In the ninth, particularly preferred moiety of compounds A, these compounds are alkanes with three methyl or ethyl substituents which are located (i) on vicinal internal carbon atoms and have a total of 4-6 carbon atoms;

or (ii) with a total of three carbon atoms in the specified substituents and one terminal CHMe2 group;

or (iii) with a total of three carbon atoms in the listed substituents and containing only secondary internal carbon atoms in the longest carbon chain.

In this moiety, compounds (i) and (ii) are preferred, especially those with geminal methyl groups on the intrachain carbon atom.

The preferred lead-free composition of MON value at least 81 or 85 and RON value at least 91 or 94 comprises component (a), a total of at least 15% of one or more branched alkane compounds A ¹ of 8-12 carbon atoms (especially 4-6 backbone carbon atoms) with three methyl or ethyl backbone branches and at least 2 backbone carbon atoms which are secondary and / or tertiary carbon atoms (with, of course, no more than one tertiary carbon backbone) , provided that if there are only 2 such carbon atoms, then one is tertiary, there is a minimum of at least 10% (by volume of the composition) of at least one individual compound a ¹

GB 192 296 B1, and component (b), the type and content defined above, especially _one provided as above. In the above component A ^1, which may be identical or different from A, can thus be ten moieties at internal backbone (ie. Non-terminal) carbon atoms which are: (i) one group tertiary and one secondary, especially (ii) with tertiary and secondary vicinal carbons, or (iii) one tertiary, one secondary and one primary, especially with vicinal tertiary and secondary carbons, or vicinal or non-vicinal secondary carbons, or (iv) three groups with secondary carbons with which at least two vicinal atoms, e.g. three with three vicinal atoms. The compounds A ¹ usually are free from 2 primary internal backbone carbon atoms on vicinal carbons, ie. As in 1,2-ethylene group. Preferably, any primary internal backbone carbon atoms are not between, e.g. adjacent on both sides, a tertiary and / or secondary carbon on one side and a secondary carbon on the other side. Especially at least the said 2 backbone carbon atoms in compounds A ¹ are vicinal.

Other eleventh moiety are compounds A ¹ which contain (provided that they have only three groups of branching) (i) as one end of the backbone a group of formula CHR ¹ R ^2, wherein each of R ¹ and R ^2, which are identical or different, is a methyl or ethyl group or (ii) as one end of the skeleton a group of formula CR ¹ R ² R ³ , wherein R ¹ and R ² are as defined above and R ³ is methyl or ethyl. Compounds A ¹ having both (i) and (ii) ^{are preferred, especially if the CHR 1} R ^{2 group} is CHMe 2, if the compound has 8 carbons or a 5 carbon backbone, and if all internal carbon atoms in the backbone chain are secondary or tertiary (including a total of 3 branching groups).

The compounds A or A ¹ may have a boiling point of 129-150 ° C under a pressure of 100 MPa and 110-129 ° C or 90-109 ° C. More particularly the boiling point is preferably 105 ° C, e.g. 105-175 ° C, provided that compound A is not 2,2,3-trimethylpentane, or is at least 112 ° C, especially 112-175 ° C.

₁

Preferably, the compounds A or A ¹ may have three branches are methyl and / or ethyl 4-6 carbon backbone, and especially the proportion of carbon atoms in branches to carbon atoms in the chain backbone of at least 0.55: 1, especially 0,55- 0.9: 1, e.g. 0.63-0.9: 1. The compounds usually contain 9 carbon atoms, unless the above proportion is 0.63 or 0.75.

Preferred compounds are 2,2,3-trimethylpentane (A3), 2,2,4-trimethylentane (isooctane) (A4), 2,2-dimethyl-3-ethylpentane (A5), 2,3,3-triethylentane (A6) ), 2,4-dimethyl-3-ethylpentane (A8) and 2,3,4-trimethylpentane (A9). The branched hydrocarbon may also not be 2,2,4-trimethylpentane and / or 2,2,3-trimethylpentane. The compounds A and A ¹ are known compounds or may be prepared according to published literature, or are novel and can be prepared by conventional methods known per se from the literature (eg. As disclosed in Kirk Othmer Encyclopedia of Chemical Technology, 3rd Ed., Publ . Wiley). Examples of suitable preparation methods are the known carbon-carbon coupling techniques to form alkanes The technique may involve the reaction of one or more, usually 1 or 2, alkyl chlorides, bromides or iodides with group IA, IIA, IB or IIB elemental metals of the FACotton Advanced Inorganic Chemistry Periodic Table and G. Wilkinson, Interscience, New York, eds. 2, 1996, especially sodium, magnesium or zinc. The alkyl halide usually has a branched chain of 3-6 carbons, especially with methyl or ethyl branches, and especially a halogen atom attached to the CMe2 group in one of the alkyl halides. Preferably the halide has the formula MeCMe2X or EtCMe2X where X is Cl, Br or Ia the other halide is a secondary halide, e.g. of formula RR ^I CH-X where each R and R ¹ is methyl or ethyl such as isopropyl halide or sec-butyl or sec-amyl, or a primary branched alkyl halide, e.g. of formula R ^II CH2X, wherein R ^II is a 3-5 carbon branched alkyl group with methyl or ethyl branches such as isopropyl, isobutyl and isoamyl. Alternatively, both halides may be secondary, e.g. of formula RR ^I CHX as defined above and R ^III R ^IV CHX where R ^III is methyl or ethyl and R ^IV is defined as for R ^II , such as isopropyl, or one may be secondary (as above) and one primary, e.g., methyl or ethyl halide. Methods of coupling optimum for any particular compound A or A ¹ depend on availability of the precursor - an alkyl halide so that in addition to the above, coupling of methyl or ethyl halides with branched alkyl halides of 6-9 carbons may also be used. The alkyl halide (s) may react with each other in the presence of a metal (as in the Wurtz reaction with sodium) or one may react first with the metal to form an organometallic compound, e.g. a Grignard or organzinc reagent, and then the organometallic compound is

Reacted with another alkyl halide. If desired, the Grignard reagent may be reacted in the presence of a Group IB or IIB metal such as silver, zinc or copper (especially highly active copper). If desired, the Grignard reagent of one or both of the alkyl halides can be reacted with the latter metal to form another metalalkyl compound, e.g., silver alkyl or copper alkyl compounds, which can disproportionate to the conjugated alkane. Grignard reagents also react with copper (I) halides to form copper-alkyl compounds for disproportionation. Finally, an organometallic compound in which the metal is one of group IA or IIA, e.g. Li or IIg, can be coupled by reaction with a copper (I) complex to give a conjugated alkane.

The above organometallic reactions are usually carried out under inert conditions, i.e. anhydrous and free of oxygen, e.g. under dry nitrogen. They are usually carried out in an inert solvent, e.g. dry hydrocarbon or ether. Upon completion of the reaction, any residual organometallic material is decomposed by adding a compound having active hydrogen, e.g. water or an alcohol, and the alkanes are distilled off, either directly or after extraction between the organic phase and the aqueous phase.

Examples for the preparation of highly branched alkanes are disclosed in F.L. Howard, et al., J. Res. Nat. Bur. Standards Research Paper RP 1779, vol. 38, March 1947, pp. 365-395. We hereby refer to the above document.

The crude alkanes produced according to the above methods may be used as such in the compositions of the invention or may be further purified, e.g. by prior distillation.

If desired, compounds with especially 8 carbon atoms can be obtained by fractionated distillation of refinery streams, e.g. crude gasolines or alkylation products, e.g. alkylation of 3-5 carbon isoalkanes with 3-5 carbon alkanes as described above.

Other known methods for preparing alkanes A or A ¹ reactions are aluminum alkyls, for example. Grignard compounds with carbonyl compounds such as aldehydes, ketones, esters, or anhydrides to give the carbinols branched chain, which are dehydrated to the corresponding olefin, which is hydrogenated to alkanes. Thus, 2,3,4-trimethylpentane can be made from isopropylmagnesium bromide and methylisopropyl ketone (followed by dehydration and hydrogenation) and 2,2-dimethyl-3-ethylpentane from ethylmagnesium chloride and diisopropyl ketone.

The composition according to the invention is used to prepare a refined unleaded gasoline that contains at least one gasoline conditioner, e.g. an additive to motor or aviation gasoline, improving the properties of the gasoline. In this specification, gasoline with additives is also referred to as "prepared gasoline."

Component (a) may be present in an amount of 5-95% or 8-90%, such as 10-90% or 15-65%, e.g. 20-55% or 10-40%, such as 20-35% by volume or 40 -90%, such as 40-55% or 55-80%, or 8-35%, such as 8-20% by volume. Unless otherwise stated, all percentages herein are percentages by volume and the reported numerical ranges of amounts in the composition or gasoline for 2 or more components include all subcombinations of all ranges for all components.

The composition according to the invention may also contain as component (b) at least one 5-10 carbon saturated hydrocarbon, especially C7 or C8 branched chain compounds, e.g. iso C7 or iso C8. The hydrocarbon may be substantially pure, e.g. n-heptane, isooctane or isopentane, or a mixture, e.g. a distillation product or a reaction product from a refining reaction, e.g. an alkylate. The hydrocarbon may have a Motor Octane Number (MON) of 0-60, but preferably has a MON of 60-96, such as the isomerization product (bp 25-80 ° C). The research octane number RON may be 80-105, e.g. 95-105, while the ROAD value (mean MON and RON) may be 60-100.

Component (b) which is different from component (a) may include a hydrocarbon component with a boiling point (preferably a final boiling point) of at least 82 ° C, e.g., 85-150 ° C, but less than 225 ° C, e.g. than 170 ° C or 160 ° C, and typically has a Motor Octane Number of at least 92, e.g., 92-100; Such components are usually alkanes with 7-10 carbons, especially 7 or 8 carbons, especially those having at least one branch in their alkyl chain, especially 1-3 branches, preferably on the internal carbon atom, and containing at least one -C (CH3) group ) 2-.

The total amount by volume of component (b) (or the amount by volume of mixtures containing component (b), such as the sum of all of the following (if any) (i) - (iv)), such as: (i) catalytic reforming products,

(Ii) heavy white spirit catalytic cracking products, (iii) white spirit catalytic cracking products, and (iv) crude gasoline in the composition in the composition typically is 10-80%, e.g. 25-70%, 40-65 % or 20-40% with higher percentages typically used with the lower percentage of component (a).

Component (b) may be a mixture of liquid saturated hydrocarbons, e.g. a distillation product, e.g. kerosene or crude gasoline, or a reaction product from a refining reaction, e.g. an alkylate containing the full alkylate range (bp 30-190 ° C), isomerization product (bp 25 -80 ° C), light reforming product (bp 20-79 ° C) or light hydrocracking product. The mixture may contain at least 60% or at least 70% w / w, e.g. 60-95 or 70-90 w / w. liquid aliphatic saturated hydrocarbon.

Compositions of the invention may contain mixtures of component (a) e.g. an alkylate fraction of 15-100 ° C with a full boiling range alkylate (i.e. FBP greater than 170 ° C, e.g. 190 ° C) in a ratio of 9: 1 to 1 : 0, especially 5-9: 5-1 or 1-3: 9-7. If desired, such mixtures can be prepared by dividing the full range alkylate into first and second portions, the first portion being distilled to provide the desired fraction, and then the fraction mixed with the second portion. The remainder of the fractions may be used otherwise as described above.

The volumetric amounts in the composition according to the invention of the mixtures of component (b) (mainly fractions of liquid aliphatic saturated hydrocarbons, e.g. total isomerization product, full range of alkylate, kerosene and crude naphtha (in each case (if present) in the composition) may be 4-60 %, such as 4-25% or preferably 10-55%, such as 25-45% The full range of alkylate or crude naphtha is preferably present in component (b) optionally in combination, but preferably in the absence of the remainder, especially in an amount of 2-50%. such as 10-45%, e.g. 10-25%, 25-45% or 25-40% The compositions of the invention may also contain kerosene, e.g. at 0-25% by volume, such as 2-25%, 10-25 % or 2-10%.

The compositions may contain as component (c) a hydrocarbon component which is a 4-6 carbon saturated aliphatic hydrocarbon and which has a boiling point lower than 80 ° C at atmospheric pressure, such as 20-50 ° C, and especially has a motor octane number. greater than 88, especially at least 90, e.g. 88-93 or 90-92. Examples of the hydrocarbon component include 4 or 5 carbon alkanes, especially isopentane, which may be substantially pure or may be the crude hydrocarbon fraction from reforming or isomerization containing at least 30%, e.g. 30-80%, such as 50-70%, with the main impurities are up to 40% monomethylpentanes and up to 50% dimethylbutanes. The hydrocarbon component may be an alkane with a boiling point (at atmospheric pressure) of -20 ° C to + 20 ° C, e.g. n- and / or isobutane optionally mixed with a C5 alkane at 99.5: 0.5 to 0.5: 99.5, e.g., 88:12 to 75:25. N-butane alone or mixed with isopentane is preferred, especially in the above proportions, and especially with a volumetric amount of butane in the composition of up to 20%, such as 1-15%, e.g. 1-8, 3-8 or 8-15%.

Cycloaliphatic hydrocarbons, e.g. of 5-7 carbons, such as cyclopentane or cyclohexane, may be present, but usually in amounts less than 15% of the total, e.g. 1-10%.

The volumetric amounts in the composition of the total of isomerization product, full range alkylate, kerosene, crude gasoline, 4-6 carbon liquid aliphatic hydrocarbon (as defined above) and cycloaliphatic hydrocarbon (in any case if present) may be 5-60%, such as 8-25 %, 15-55% like 30-50%.

The compositions of the invention also preferably contain as component (d) at least one olefin (especially with one double bond in the molecule), which is a liquid alkene of 5-10, e.g. 6-8 carbons, such as a linear or branched alkene, e.g. pentene, isopentene, hexene, isohexene or heptene, or 2-methyl-2-pentene, or a mixture containing aikenes, which may be made by cracking, e.g. catalytic cracking or thermal crude oil residues, e.g. atmospheric or vacuum residues; the mixture can be a heavy or a light catalytic cracker of mineral spirits (or a mixture thereof). Cracking may be steam assisted. Other examples of olefin-containing mixtures are "C6 bizomers, catalytic polymerate, and dimate." The olefinic mixtures usually contain at least 10% w / w. olefins, such as at least 40%, such as 40-80% w / w. The preferred mixtures are (xi) steam-cracked white spirit (xii) catalytically cracked white spirit (xiii) C6 bisomer and (xiv) catalytic polymerate, although optionally catalytically cracked white spirit is most preferred. The amounts of the total composition of olefin mixtures, especially the sum of (xi) - (xiv) (if present) can be 0-55, e.g. 10-55 or 18-37, such as 23-35 or 20-55, such as 40-55%

PL 192 296 B1 or 23-40%. The amounts of (xi) and (xii) (if present) in total in the composition are preferably 18-55, such as 18-35, 18-30 or 35-33% (by volume).

The olefin or mixture of olefins typically has a MON value of 70-90, typically a RON value of 85-95 and a ROAD value of 80-92.

The amount by volume of olefin (s) in total in the gasoline composition according to the invention may be 0% or 0-30%, e.g. 0.1-30%, such as 1-30%, especially 2-25, 5-30 (especially 3- 10), 5-18.5, 5-18 or 10-20%.

Preferably the composition comprises at least 1% olefin and a maximum of 18%, or especially a maximum of 14%, but may be substantially free of olefins.

The compositions may also contain as component (e) at least one aromatic compound, preferably an alkyl aromatic compound such as toluene or o-, m-, or p-xylene, or a mixture thereof, or trimethylbenzene. The flavors can be added as individual compounds, e.g. toluene, or they can be added as flavor mixtures containing at least 30% w / w. aromatics, such as 30-100%, especially 50-90%. Such mixtures may be made from catalytically reformed or cracked naphtha obtained from heavy kerosene. Examples of such mixtures are (xxi) catalytic reforming product and (xxii) heavy reforming product. The amounts of the individual compounds, e.g. toluene, in the composition may be 0-35%, such as 2-33%, e.g. 10-33%, while the amounts of the aromatic mixtures, especially the sum of the reformed products (xxi) & (xxii) (if any) in of the composition may be 0-50%, such as 1-33%, e.g. 2-15% or 2-10% or 15-32% v / v and the total amount of reformed product (xxi), (xxii) and added single compounds (e.g. toluene) may be 0-50%, e.g. 0.5-20% or 5-40, such as 15-35 or 5-25% v / v.

The aromas typically have a MON value of 90-110, e.g. 100-110, and a RON value of 100-120, such as 110-120 and a ROAD value of 95-110. The amount by volume of aromatics in the composition is typically 0% or 0-50%, such as less than 40% or less than 28%, or less than 20%, such as 1-50%, 2-40%, 3-28%, 4-25%. , 5-20% (especially 10-20%), 4-10% or 20-35%, especially toluene. The gasoline composition also may be substantially free of aromatic compound. Aromatic amounts below 42%, e.g. below 35% or especially below 30%, are preferred. Preferably the amount of benzene is less than 5%, preferably less than 1.5% or 1%, e.g. 0.1-1% of the total volume or less than 0.1% of the total weight of the composition.

The compositions may also contain as component (f) at least one oxygenate octane booster, typically with a motor octane number of at least 96-105, e.g. 98-103. The oxygenate may be any organic liquid molecule containing and preferably consisting of CH and at least one oxygen atom, e.g. less than 225 ° C. The octane adjuvant is usually an ether, e.g. a dialkyl ether, especially asymmetric, preferably one in which the alkyl has 1-6 carbons, especially one in which the alkyl is a branched alkyl of 3-6 carbons, especially tertiary alkyl, especially 4- 6 carbons such as tert-butyl or tert-amyl, the remaining alkyl having 1-6, e.g. 1-3, carbons and is especially linear, such as methyl or ethyl. Examples of such oxygenates include tert-butyl methyl ether (MTBE), tert-butyl ethyl ether and tert-amyl methyl ether. The oxygenate may also be an alcohol of 1-6 carbons, e.g. ethanol. The oxygenate may also be an organic carbonate, e.g. a dialkyl carbonate of 1-3 carbon atoms in each alkyl, e.g. dimethyl carbonate.

The amount by volume of the oxygenate may be 0 or 0-25%, such as 1-25%, 2-20%, 2-10% or 5-20%, especially 5-15%, but preferably less than 3%, such as 13% ( especially MTBE and / or ethanol). The oxygenate may also be substantially absent from the composition or gasoline of the invention.

Thus, the present invention provides an unleaded blend composition of MON value at least 81 or 85 and RON value at least 91 or 94 which comprises (a) a total of at least 15% of one or more branched hydrocarbon compound A or A ^1, and a minimum of at at least 5% of at least one individual compound A or A ¹ and (b) at least 20% of at least one different liquid hydrocarbon of bp 60-160 ° C having a MON value of at least 70 and RON value at least 90 especially when (b ) is not covered by the definition of a or a ¹ especially when (a) is trimethyl pentane. Examples of liquid hydrocarbons are paraffins such as 4-8 carbon linear or branched chain alkanes such as isobutane, butane, isopentane, dimethylalkanes such as 2,3-dimethylbutane, cycloalkanes such as cyclopentane and cyclohexane, aromas and olefins.

Another lead-free blend composition of the invention having a MON value of at least 81 or 85 and a RON value of at least 91 or 94 comprises component (a) as above and as component (b) at least 20% of at least 20% of crude kerosene, an alkylate isomerization product ( t 25-80 ° C),

PL 192 296 B1 heavy reformer, light reformer (tp 20-79 ° C), hydrocracking product, aviation alkylate (tp 30-190 ° C), crude gasoline, cracked white spirit, such as heavy or light catalytically cracked white spirit and steam cracked white spirit. Raw products are produced directly from crude oil by atmospheric distillation. Kerosene may be light kerosene, i.e. 30-90 ° C, medium kerosene, m.p. 90-150 ° C or heavy kerosene, e.g. 150-220 ° C.

In the compositions according to the invention, the amount of at least one of the individual compounds A or ₁

A ¹ is usually at least 5% or at least 10 or 15%, such as 5-60%, eg. 15-60% or 8-25%, 20-35%, or 30-55% or 2-10%. The amount of compound A4, if present, is usually at least 10% of the composition. The total amount of trimethylpentanes in the blend is preferably less than 69% of the blend, but preferably at least 26% (especially if the amount of flavors is less than 17%). When the 9 or 10 carbon alkane is (a), the amount of 2,2,4-trimethylpentane is especially less than 70 or 50%. There may be more than one such compound A or A ^1, eg. Higher or lower RON in weight ratios of 9: 1 to 0.5: 99.5, such as 0.5: 1 to 5: 1 or 5:95 to 20 80, particularly for mixtures of compounds of higher or lower boiling points (atmospheric pressure), for example. those in which the compounds a and / or a ¹ have boiling points differing by at least 10 ° C, eg. at least 40 ° C such as 10-70 ° C or 20-50 ° C, the amounts being as disclosed above. Total amounts of all compounds A and A ¹ (if present) in the mixture may be 15-70, for example. 15-60, 15-40 or 30-55% or 40-60%.

The blend also may contain predominantly aliphatic refinery streams such as kerosene, crude gasoline (also called light kerosene, mp. 25-125 ° C), alkylate, and isomerization product. The total amount of these may be 10-70%, such as 10-30, 30-70 or 35-65%. The amount of kerosene may be 0-70% or 1-70%, such as 1-30, 30-70 or 35-65%, while the amount of light kerosene may be 0 or 1-70, such as 1-20 or especially 30-65%. , and the amount of medium kerosene may be 0 or 1-55, such as 3-20 or 15-55%. The volume ratio of light to medium kerosene can be 50: 1 to 1:50, such as 0.5-20: 1 or 1: 0.5-50. The amount of alkylate or isomerization product (if present) may be 0.5-20%, such as 1-10%, while the amount of hydrocracking product may be 0.5-30%, e.g. 10-30%.

The blends of the invention typically contain a total of at least 70% saturated compounds, such as 70-98% or 70-90% or 90-98%.

If desired, and especially in the case of aviation gasoline, the blends may contain a hydrocarbon component which is a saturated aliphatic hydrocarbon of 4-6 carbons and which has a boiling point below 80 ° C at atmospheric pressure, such as 20-50 ° C, and especially motorized an octane number greater than 88, especially at least 90, e.g. 88-93 or 90-92. Examples of the hydrocarbon component include 4 or 5 carbon alkanes, especially isopentane, which may be substantially pure or the crude hydrocarbon fraction from reforming or isomerization containing at least 30%, e.g. 30-80%, such as 50-70%, with the main impurity being make up 40% monomethylpentanes and up to 50% dimethylbutanes. The hydrocarbon component may be an alkane with a boiling point (at atmospheric pressure) -20 ° C to + 20 ° C, e.g. niisobutane, possibly in blends with a C5 alkane 99.5: 0.5 to 0.5: 99.5, e.g. 88:12 to 75:25. N-butane alone or mixed with isopentane is preferred, especially in the above proportions, especially with a volume of butane in the composition of up to 20%, such as 1-15%, e.g. 1-8, 3-8 or 8-15%, especially 1-3.5%.

The hydrocarbon component boiling less than 80 ° C, in particular isopentane, may also be present in the compositions according to the invention which contain at least one compound A or A ¹ 1 having at least 10 carbon atoms. Relative amounts of these compounds A or A ¹ to the low boiling component, for example. Isopentane, may be 1-9: 9-1 such as 5-9: 5-1, especially when it is less than 20% of A or A ¹ in the composition.

Cycloaliphatic hydrocarbons, e.g. with 5-7 carbon atoms, such as cyclopentane or cyclohexane may be present, but usually in amounts less than 15% of the total, e.g. 1-10%.

The blend of the invention comprises at least one component (a) and component (g) and (optionally (c) to (f), and the processed unleaded gasoline also includes at least one gasoline additive, e.g. motor gasoline or aviation gasoline additive, for example, as listed in ASTM D-4814, the content of which is hereby referred to, or prescribed by an administrative body, e.g., the US California Air Resources Board (GARB) or the Enviromental Protection Agency (EPA). These additives are distinct from liquid ingredients Such additives may be unleaded as disclosed in Gasoline and Diesel Fuel Additives, K. Owen, publ. J. Wiley, Chichester, UK, 1989, chapters 1 and 2, USP 3955938, EP 0233250 or EP288296, to which we are hereby referenced The additives may be pre-combustion or incineration additives.

PL 192 296 B1

Examples of additives are antioxidants such as the amine or phenolic type, corrosion inhibitors, antifreeze agents such as glycol ethers or alcohols, engine cleaners such as succinimide, polyalkylene amines or polyetheramines, and antistatic additives such as ampholytic surfactants , metal deactivators such as the thioamide type, surface ignition inhibitors such as organophosphorus compounds, combustion enhancing agents such as alkali metal and alkaline earth metal salts, valve seat anti-burnout agents such as alkali metal compounds, e.g. sodium or potassium salts such as borates or carboxylates, e.g. sulfosuccinates, and coloring agents such as azo dyes. One or more (e.g. 2-4) additives of the same or different kinds may be used, especially combinations of at least one antioxidant and at least one detergent additive. Antioxidants such as one or more hindered phenols, e.g. those with a tertiary butyl group at one or both positions ortho to the phenolic hydroxyl group, are preferred, especially as disclosed in Example 1 below. In particular, additives may be present in the compositions in amounts of 0.1-100 ppm, e.g. 1-20 ppm of each, usually antioxidant, especially one or more sterically hindered phenols. Total amounts of additives usually do not exceed 1000 ppm, e.g. 1-1000 ppm.

The compositions and gasolines are free from organoleaded compounds and usually manganese additives such as manganese carbonyls.

The compositions and gasolines may contain up to 0.1% sulfur, e.g. 0.000-0.02%, especially 0.002-0.01% w / w.

Motor gasolines containing an unleaded composition according to the invention, especially gasolines based on distillation fractions, e.g. alkylate fractions, typically have a MON value of 80 to less than 98, such as 80-95, 83-93, 85-90 or 93-98. The RON value is usually 90-115, e.g. 102-115 or preferably 90-102, preferably 90-100, e.g. 90-99, such as 90-93, e.g. 91 or 93-98, e.g. 94.5-97 , 5 or 97-101, with the ROAD being typically 85-107, e.g. 98-106 or preferably 85-98, such as 85-95, e.g. 85-90 or 90-95 or 95-98. Preferred gasoline compositions have MON 80-83, RON 90-93 and ROAD 85-90, or MON 83-93, RON 93-98 and ROAD 85-95 or MON 85-90, RON 97-101 and ROAD 91-96. The net calorific value of gasoline (also called specific energy) is usually at least 18,000 Btu / lb, e.g. at least 18,500, 18,700 or 18,900, such as 18,500-19,500, such as 18,700-19,300 or 18,900-19,200; the calorific value may be at least 42 MJ / kg, e.g. at least 43.5 MJ / kg, such as 42-45 or 43-45, or such as 43.5-44.5 MJ / kg. Gasoline typically has a boiling range (ASTM D86) of 20-225 ° C, especially with at most 5%, e.g. 0-5% or 1-3% boiling in the range 161-200 ° C. Gasoline is typically such that at 70 ° C at least 10% will evaporate, while 50% will evaporate upon reaching a temperature in the range 77-120 ° C, preferably 77-116 ° C, and up to 185 ° C a minimum of 90% will evaporate. Usually also gasoline is such that 8-50% of gasoline, e.g. 10-50%, can evaporate at 70 ° C, 40-74% at 100 ° C, 70-99.5%, e.g. 70-97%, in 150 ° C and 90-99% of gasoline can evaporate at 180 ° C; preferably at least 46%, e.g. 46-65%, evaporate at 100 ° C. The Reid's vapor pressure of gasoline at 37.8 ° C as measured by ASTM D323 is typically 30-120, e.g. 40-100, such as 61-80 or preferably 50-80, 40-65, e.g. 40-60 or 40- 50 kPa.

Unleaded motor gasolines preferably contain component (a) and have a RON value of at least 98, a MON value of 87.8, an RVP below 60 kPa, e.g. 40-60 kPa, less than 35% aromatics, less than 15% olefins, 10-45 % is evaporated at 70 ° C, 46-60% is evaporated at 100 ° and more than 88% is evaporated at 150 ° C. Their density is preferably at least 0.71, e.g. 0.71 to 0.78, especially at least 0.7122 or at least 0.72, such as 0.7122 to 0.7264 kg / l.

Gasoline compositions, especially those based on branched chain alkanes for component (a), typically have a MON value of 80 to 94, such as 85-90, or 90-94. The RON value is typically 90-105, e.g. 98-102, or 93-98, e.g. 94.5-97.5 or 97-101, while the ROAD value is typically 85-102, e.g. 98-102 or 85- 95. Preferred gasoline compositions have MON 83-93, RON 93-98 and ROAD 85-95, or MON 85-90, RON 94-101 and ROAD 89-96. The net calorific value of gasoline (also called specific energy) is typically as disclosed above and the boiling point ranges measured according to ASTM D86 as well as RVP.

Gasoline compositions, when free from oxygenates, typically have an H: C atom ratio of at least 1.8: 1, e.g., at least 2.0: 1, or at least 2.1 or 2.2: 1, such as 1.8- 2.3: 1 or 2.0-2.2: 1. Preferably, the gasoline composition meets the following criteria.

Atom H: C x [1 + oxy] x [net heat of combustion + ROAD]> y 200

Where the H: C atom is a fraction - the ratio of hydrogen to carbon atoms in the hydrocarbons in the composition, oxy is the molar fraction of oxygenate, if present in the composition, the net heat of combustion is the energy derived from the combustion of 1 Ib (454 g) of fuel (gaseous) in oxygen yielding gaseous water and carbon dioxide expressed in units of Btu / lb [MJ / kg times 430.35] and y is at least 350, 380, 410 or 430, especially 350-440, e.g. 380 = 420, especially 400-420.

Preferably, motor gasoline comprises 10-90% component (a), 10-80% component (b), 0-25% kerosene, 0-15% butane, 5-20% olefins, 3-28% aromatics and 0-25 % oxygenates, especially with 5-20% aromatics and 5-15% olefins.

In particular, motor gasoline contains 8-65% of component (a), especially 15-35% of this component; 0.1-30% olefins, e.g. 2-25%, especially 3-14% olefins; 0-35% of aromatics, such as 0-30%, e.g. 3-35 or 5-20 (especially 5-15%), or 20-30% of aromatics; and 5-50% mixtures of component (b), e.g. 10-45%, especially 20-40%. Such gasolines may also contain oxygenates such as MTBE, especially in an amount below 3%, e.g. 0.1-3%, they may also contain benzene, especially below 1.0% benzene, e.g. 0.1-1%, and may contain olefins, especially less than 18% olefins, e.g. 0.1-15%. Such gasolines preferably have RON 96-99, MON 86-90 and ROAD 91-94.5 values.

Examples of motor gasolines are those with 5-25% component (a), 5-15% olefins, 15-35% aromatics and 40-65% component (b), especially 15-25% component (a), 7-15% olefins, 15-25% aromatics and 45-52% of a mixture of component (b) with a RON value of 96.5-97.5 or 5-15% of component (a), 7-15% olefins, 15-25% aromatics and 55 -65% of the compound (b) having a RON value of 94.5-95.5.

Examples of motor gasolines are those with 1-15%, e.g. 3-12% butane, 0-20% e.g. 5-15% ether, e.g. MTBE, 20-80, e.g. 25-70% refinery liquids (typically C6 -C9) mixed streams (except kerosene) such as mixtures of the above mentioned (i) - (iv)), 0-25% e.g. 2-25% kerosene, 5-70% e.g. 15-65% of component (a) o RON 93-100, e.g. 94-98, MON 80-98 e.g. 83-93 or 93-98 and RVP 40-80, such as 40-65 kPa. Such gasolines typically contain 1-30% e.g. 2-25% olefins and 2-30% e.g. 4-25% aromatics. Olefin amounts of 15-25% are preferred for RON values of 94-98, e.g. 94-96 and 2-15% e.g. 2-7% for RON values of 96-100, such as 96-98.

Other examples of fuel compositions contain 8-18% of component (a), 10-50% e.g. 25-50% of the total mixture of component (b), 5-40% e.g. 20-35% of the total mixture of aromatics, 15-60% e.g. 15-30% or 40-60% of the total olefin mixture and 0-15% of the total oxygenates e.g. 3-8% or 8-15%. Particularly preferred compositions have 8-18% of component (a), 25-40% of total blend of component (b), 2035% of total aromatics, and 15-30% of total olefin, or 8-18% of component (a), 15-40% of total blend of component (b). total blend of component (b), 3-25% of total flavor blend, and 40-60% of total olefin blend.

Further examples of fuel compositions contain 20-40% of component (a), 8-55% of the total mixture of component (b), e.g. 5-25% or 35-55%, and 0 or 5-25%, e.g. 18-25 % of total aromatics mixture, 0-55, especially 10-55 or 40-55% of total olefin mixture, and particularly preferred compositions have 20-40% of component (a), 5-25% of total mixtures of component (b), 3-25 % of the total mixture of flavors and 40-60% of the total olefin blend or 20-40% of component (a), 35-55% of the total mixture of component (b), 15-30% of the total mixture of flavors and 0-15% e.g. 5-15 % of the total olefin mixture or especially 20-40% of component (a), 25-45% or 30-50% of the total mixture of component (b), 2-15% of the total mixture of aromatics, 18-35% of the total mixture of olefins and especially 3- 10% or 5-18% olefins and 10-35%, such as 10-20% aromatics (e.g. 10-18%).

Other examples of fuel compositions contain 30-55% e.g. 40-55% of component (a), 5-30% of total mixture of component (b), 0-10% of total mixture of aromatics, 10-45% of olefin mixture and 0-15% oxygenates, especially when the sum of the oxygenates and the olefin mixture is 20-45%. Other examples of fuel compositions contain 55-70% of component (a), 10-45% of the total of component (b), e.g. 10-25% or 35-45% and 0-10%, e.g. 0 or 0.5-5 % of the total mixture of flavors and 0-30% of the total olefin mixtures, e.g. 0 or 15-30%, especially 55-70% of component (a), 10-25% of the total of component (b) 0 or 0.5-5% of the total aromatics mixture and 15-30% of the total olefin mixture.

Particularly preferred examples of fuel compositions contain 15-35% e.g. 20-35% of component (a), 0-18.5% e.g. 2-18.5% olefins, 5-40% e.g. 5-35% aromatics, 25 -65% saturated compounds and less than 1% benzene, and 18-65% e.g. 40-65% of component (a), 0-18.5% e.g. 5-18.5% olefins, 5-42% e.g. 5 -28% aromatics, 35-55% saturated compounds and less than 1% benzene.

The other fuel composition may contain 25-40%, e.g., 30-40%, such as 35%, alkylate (especially a full bp alkylate with an IBP of 30 ° C or greater and a FBP greater than 165 ° C), 10-25% e.g. 15-25%

Such as 20% isomerization product, 10-25% e.g. 15-25% e.g. 20% light hydrocracking product and 20-35% e.g. 20-30% e.g. 25% of component (a) and optionally 0-5% . Such a composition is preferably substantially paraffinic and substantially free of olefins and aromatics.

Another gasoline composition contains 2-20% e.g. 5-15% of component (a), especially 15-100 ° C alkylate fraction, 20-40% e.g. 25-35% full boiling alkyl e.g. FBP 175- 200 ° C (especially when the sum of component (a) and alkylate is 35-45%), 25-40% olefin mixtures such as steam cracked white spirit, 5-205 e.g. 7-15% reforming product, 10-25 % e.g. 12-20% toluene and 0.1-3% e.g. 0.5-2.0% butane. A preferred gasoline, e.g. the latter, typically has RON 98-101, MON 86-89 E100 ° C (% evaporation at 100 ° C) 45-55 e.g. 48-52, flavors 30-40%, such as 30-35% , olefins 3-15% e.g. 5-10% and a total saturated 50-65% e.g. 55-60%. Such a composition is devoid of oxygenate additives. Toluene can be replaced by an equal volume of heavy reformer.

Another gasoline composition of particular importance comprises 0.5-5% e.g. 2-4% butane, 10-30% e.g. 15-25% full range alkylate (e.g. FBP 175-200 ° C), 10-40% such as 20-35% of component (a), especially alkylate fractions 110-115, 115-125, 15-160 or 15-100 ° C (especially for total alkylate and component (a) 35-60% e.g. 40-55%) , 30-50% catalytic reformer and 5-15% bisomer, MON 87-90, RON 98-101 and ROAD 93-95. The composition is also free of oxygenate.

Other motor fuel compositions may have different anti-knock index (also called ROAD index) ranges which is the average of MON and RON.

For ROAD 85.5-88.5 indicators, the compositions may contain 8-30% of component (a), e.g. 15-30% and 10-50%, e.g. 20-40% of the total mixture of component (b), 5-30% e.g. 5-20% of total olefins and 10-40 e.g. 15-35% of total aromatics or 8-30% of component (a), 10-50% of total mixture of component (b), 5-40% of total flavor mixtures e.g. 20-30% and 10-60% e.g. 30-55% of the total olefin mixtures.

For ROAD 88.5-91.0 indicators, the compositions may contain 5-25% (or 5-15%) of component (a), 20-45% of the total mixture of component (b), 0-25%, e.g. 1-10 or 10 -25% of total olefins and 10-35% e.g. 10-20% or 20-35% of total aromatics or 5-25% (5-15%) of component (a), 20-45% of the total mixture of component (b), 0-35% of total flavor mixtures e.g. 1-15% or 15-35% and 5-65% e.g. 5-30 or 30-65% of total olefin mixtures.

For ROAD 91.0-94.0 indicators, fuel compositions may contain 5-65%, e.g. 5-20, 20-30, 30-65 or 40-65% of component (a) and 5-40% (5-35% ) e.g. 5-12 or 12-40% (12-30%) of the total mixture of component (b), 1-30% e.g. 1-10 or 10-25% of the total olefins and 5-55% e.g. 5-15 or 15-35 or 35-55% of total aromatics or the above amount of component (a) with 0-55 e.g. 0.5-25% e.g. 10-25% or 25-55% aromatics and 0 or 10-60% , e.g. 10-30% or 35-60%, of the total olefinic fraction.

For ROAD 94-97.9 indicators, fuel compositions may contain 20-65% of component (a) e.g. 40-65% of component (a), 0-15% e.g. 5-15% of total olefins, 0-20% e.g. 5-20% of total aromatics and 5-50 e.g. 30-50% of the total mixture of component (b), or the above amount of component (a) and the total mixture of component (b) with 0-30% e.g. 1030% of aromatic fractions and 0 -30 e.g. 5-30% olefin fraction, or the above amounts of component (a) e.g. 20-40% of component (a), total mixture of component (b), all olefins and all aromatics with 2-15% aromatic fractions and 18 -35% olefinic fraction.

Among the preferred compositions (blends) of the invention are blends of lead-free comprising as component (a) at least 10% of one individual compound A or A ¹ and component (b) ₁ as defined above, provided that (i) is a compound A or A ¹ is trimethylpentane, the blend comprises 10-65% total trimethylpentanes, and at least 10% an alkane of 6 or 7 carbon atoms, and has a MON value of at least 70 and a RON value of at least 90, and preferably less than 5% 2.2 3-trimethyl pentane and 2,2,3-trimethyl, and (ii) when the compound a or ^A1 is an alkane of 9 or 10 carbon atoms, then blend contains at least 10% of an alkane of 6 or 7 carbons of MON at least 70 and a RON of at least 90, and preferably contains less than 5% in total 2,2,3-trimethylpentane and 2,2,3-trimethylbutane. In case of condition (i), the blend preferably comprises at least 26% (or 30%) of the total alkanes of 7 or 8 carbons with a MON of at least 70 and a RON of at least 90, and / or less than 17% of the total aromatics.

Preferred, refined (prepared) unleaded gasoline comprise at least one gasoline additive and the preferred composition (mixture) unleaded above mentioned (front section), provided that (iii) when the compound A or A ¹ is trimethylpentane, then blend contains 10-65 % of total trimethylpentanes and less than 5% of 2,2,3-trimethylpentane and 2,2,3-trimethylbutane

GB ₁ 192 296 B1, and (iv) when the compound A or ^A1 is an alkane of 9 or 10 carbon atoms, the blend preferably contains less than 5% in total of 2,2,3-trimethyl pentane and 2,2,3-trimethyl butane.

Preferred gasoline and blend compositions may have MON values of 80-94 e.g. 80-85 or 90-94, RON values of 90-105 e.g. 90-95 or 97-105, ROAD values of 85-102, compound A or A content of ¹ 30 60% eg. 40-60% (containing 1 or 2 compounds A or A ^1), total naphtha of 35-65% (eg. 35-55%) and 1-5% butane, the blends containing 1-8 % e.g. 2-6% aromatics, 0-1% olefins and 91-99% (e.g. 94-98%) saturated compounds. They are essentially aliphatic blends and high octane gasolines without the use of oxygenates such as MTBE and also essentially saturated.

Other high octane blends and gasolines may have MON values of 80-95 e.g. 85-95, RON values of 90-100 e.g. 95-100, ROAD values 85-97, content of compound A or A ¹ 30-60% e.g. 30- 50% (containing 1 or one of compounds A or A ^1), the average oil content of 5-30% and contents of total olefinic fraction such as steam cracked petroleum spirit, 30-50% and 1-5% butane, the blends containing 10 -25% aromatics, e.g. 12-18% aromatics, 4-14% e.g. 6-12% and 60-90% such as 70-80% saturated compounds. These high-octane materials are prepared without the use of oxygenates.

Further compositions and blended gasoline may have MON values of 84-90, RON values of 93-98, ROAD values of 86-94, and contain compound A or A ¹ in amount of 15-35% of the total naphtha of 40-65% and olefinic fractions such such as steam cracked white spirit 15-45% and 0 or 1-5% butane, with an aromatics content of 5-25%, such as 10-18%, an olefin content of 2-14% and a saturated content of 70-90%.

₁

Other compositions and gasolines may contain 10-35% compound A or A ^1, 30-50% oil, 10-30% of the hydrocracking product, alkylate and isomerate 2-10%, and reformate 3-12% of the product.

The present invention also provides a composition comprising component (a) and typically at least one motor gasoline additive, e.g. as disclosed above, especially with a blend of no more than a total of 5%, e.g. less than 1%, of a hydrocarbon with m.p. greater than 160 ° C and preferably less than 5%, e.g. less than 4%, of triptan or 2,2,3-trimethylpentane. Examples of component (a) are disclosed above, but is preferably an alkylate fraction, especially the 15-100 ° C fraction.

The use of component (a) allows for the production of gasoline, e.g. motor or aviation gasoline, especially with 91, 95, 97, 98 RON values, with the desired high-octane levels, but with low emissions of harmful substances during combustion, especially emissions of at least one of: total hydrocarbons, NOX, carbon monoxide and carbon dioxide, especially total hydrocarbons and carbon dioxide.

₁

Preferably, the compound A or A ^1, eg., The aforesaid compounds A3, A4, A6, or A9, or uses a fraction of the alkylate t 15-160 ° C, eg. Of bp 15-100 ° C, especially 15-60 ° C or 90-106 ° C, in unleaded gasoline, e.g. motor or aviation gasoline, with a MON of at least 80, e.g. 80 to below 98, e.g. as an additive or as a component thereof, in order to reduce the levels of harmful emissions during combustion, especially to reduce the emission of at least one of: total hydrocarbons, NOX, carbon monoxide and carbon dioxide, especially total hydrocarbons and carbon dioxide.

The presence of at least 10% of component (a) (i) allows the reduction of exhaust gas emissions during the combustion of unleaded gasoline (e.g. gasoline engine or aviation fuels with a MON of at least 80), especially during combustion in a spark ignition engine, in supercharged engines or turbocharged or naturally aspirated.

Component (a), preferably compound A or the alkylate fraction, i.e. 15-160 ° C or b.w. 15-100 ° C, especially 15-60 ° C or 90 to 106 ° C, can better reduce the emission of one or more of the above-mentioned harmful substances than the contained alkylate or mixture of flavors and oxygenate at a similar octane number, and also usually also reduces fuel consumption.

The emission of pollutants depends on the design of the vehicle and on whether the engine is hot or cold, even in engines where the exhaust gases pass through a catalytic converter before being released into the environment. In a cold engine, the effects of friction, lubricants, and the nature of fuel evaporation, among other things, differ from those in an unpredictable warm engine. Cold engines produce most of the pollutants emitted, due to the enrichment of the mixture, and in the case of vehicles with catalytic converters, the fact that the catalytic converter becomes progressively more efficient in reducing emissions as its temperature rises. In recent vehicles, the Lambda sensor above the converter controls the fuel / air ratio entering the engine, but is not effective when the engine is cold (which causes

Fuel / air ratio misregulation). Shortly after a cold start, the sensor quickly becomes effective (giving a regulated fuel / air ratio) even if the catalytic converter is not hot enough to function effectively. Thus, the cold start operation is distinct from the hot engine operation and further increases the amount of harmful emissions in the exhaust gas. The cold start period refers to a period of time or distance, which may vary depending on how the car is driven and / or environmental conditions, e.g. up to 2 km or 4 or 2 minutes, or the temperature when the engine coolant (e.g. water temperature in the cooler) remains below 50 ° C. The car's engine may also be cold if it has not been run for the 4 hours prior to starting, usually at least 6 hours prior to starting.

Gasolines with component (a), especially that which is the stream obtained by distillation as a fraction of 15-100 ° C, they give reduced emissions of harmful substances at cold start, compared to the base fuel.

Thus, the composition according to the invention makes it possible to reduce pollutant emissions during the combustion of unleaded gasoline fuels with a MON of at least 80, e.g. 80 to less than 98, when starting a cold spark ignition engine. Component (a) is preferably used in an amount that is effective to reduce emissions, especially for cold start.

In addition, gasolines can be used in spark ignition internal combustion engines. They may be used to propel vehicles by land and / or sea and / or air, the vehicle typically carrying a driver, at least one passenger and / or cargo.

₃

Size engines, which typically involve the motor gasoline is at least 45 cm ^3, for example. 45-10000 cm ^3, eg. At least 200 cm ³ and 500-10,000 cm ^3, in particular 950-2550, such as 950-1550 and 1250-1850 cm ³ or 2500-10000 cm ³ as 2500-5000 or 5000-9000 cm ^3. The engines have at least one cylinder, but preferably at least 2 or 3 cylinders, for example 3-16, especially 4-6 or 8 cylinders; each cylinder is typically 45-1250 cm ³ , e.g. 200-1200 cm ³ , especially 240-520 cm ³ or ₃

500-1000 cm ³ . The engines may be two-stroke, but are preferably four-stroke. Wankel rotary motors may be used. Gasoline engines can be used to power vehicles with two or more wheels, e.g. with 2-4 powered wheels, such as mopeds, three-wheeled mopeds and cars, vans and motor vehicles, especially those vehicles which are approved for use on public roads but also on off-road vehicles, e.g. 4WD, road sports and racing cars, off-road and circuit races. Power from the engine preferably is transferred to the drive wheels via the gearbox and clutch assembly, or other form of driveline system, to ensure transition from stationary to moving condition. The engine and drivetrain allow speeds on various roads of between 1-350 km / h, preferably between 5-130 km / h. and allows the speed to change continuously. The speed of the vehicle on the road is typically reduced by the braking mechanism fitted to the vehicle, the braking normally being by friction. The engine may be air or water cooled, and the momentum of air generated by a moving vehicle may be used to cool the engine directly or indirectly. The vehicle is fitted with a means to facilitate its change of direction, e.g. a steering wheel or joystick. Typically at least 10% of the distance traveled by the vehicle is traveled faster than 5 km / h.

Engines using aviation gasoline are typically found in reciprocating airplanes, i.e. with at least one engine driving a mechanically moving air means such as a propeller. Each engine typically drives at least one propeller drive shaft with 1 or 2 propellers. An airplane may have 1-10 propellers, e.g. 2-4. Aircraft engines usually have at least 2 cylinders, eg. 2 to 28 cylinders, each of which preferably has a capacity greater than 700 cm ^3, and

700-2000 cm ³ , e.g. 1310 cm ³ . The total capacity of the motor is usually 3700-50000 cm ^3, e.g., 33 3700 to 12000 cm ^3, for a single or twin engined passenger light aircraft, 12000 to 45000 cm ³ and four for the two planes of linear or passenger (e.g.. 15-200 passengers, like 50 to 150 passengers). Engines may have an engine power to weight ratio of at least 0.3 Hp / lb engine weight, e.g. 0.3-2 Hp / lb, and may have a power from cylinder capacity of at least 0.5 (Hp / inch ³ ), e.g. 0.5-2. The cylinders may be in series, V, H, flat (horizontally opposite) or radially around a common propeller shaft. One or more row / circle of cylinders may be used, e.g. 2 flat, 4 flat, 6 flat, V12, 2 or 3 7 cylinder wheels, etc. Each cylinder has one and more preferably at least two spark plugs. The gear system may possibly be used to drive the propeller and / or supercharger. Alternatively,

There may be exhaust turbocharging. The exhaust outlets may be individual or run to a common manifold and preferably be in the opposite direction to the flight. There may be fins on the outside of the motor for air cooling. More than 90% of the distance traveled by the engine in operation is to an altitude of approximately 150 m (500 ft) or more above sea level. Typically, more than 90% of the time of operation, the motor is operated at greater than 1,000 rpm, e.g., between 1,000 and 3,500 rpm.

The aircraft usually has at least one tank with a capacity of at least 100 liters, in particular with a total volume of at least 1000 liters.

Gasolines can be produced at a refinery by blending the ingredients to produce at least 200,000 liters / day of gasoline, such as 1-10 million liters / day. Gasoline may be distributed to many motor gasoline retail outlets, possibly through wholesalers or wholesale outlets, e.g. storage tanks, such as with a capacity of at least 2 million liters, e.g. 5-15 million liters. Distribution may be by pipeline or in tanks transported by road, rail or water, with the tanks having a capacity of at least 5,000 liters. At points of sale, e.g. gas stations, motor gasoline is distributed to many users, i.e. to vehicle drivers. , e.g., with a frequency of at least 100 or 1,000 different users per day. For aviation use, gasoline is typically produced at a refinery with a production of at least 1,000 barrels per day (or 100,000 liters / day), such as 0.1-2 million liters / day. Aviation gasoline is typically distributed by tankers by road, rail or water, or by pipelines directly to airport dispensers or storage tanks, e.g. with a capacity of at least 300,000 L, from which it is distributed by pipeline or tanks (e.g. a fuel tanker for refueling on many airplanes). e.g. at least 5 / day per tank; an airplane may have one or more on-board tanks with a capacity of at least 100 l).

Aviation gasolines containing component (a) preferably have an RVP of 38-49 kPa, 10-40% evaporation at 75 ° C, at least 50% evaporation at 105 ° C, at least 90% evaporation at 135 ° C and a sum of temperature for 10% evaporation and that for 50% evaporation greater than 135 ° C.

The present invention is illustrated by the following examples.

P r z k ł a d 1

Alkylate with an IBP of 31.9 ° C and a FBP of 191.3 ° C is a qualitative refinery product obtained commercially by HF catalyzed reaction of refinery qualitative isobutene and isobutane. This alkylate was then distilled according to ASTMD2892 providing a series of fractions with the temperatures as in Table 1 below, with analyzes giving in% w / w. main components (present in at least 1% w / w)

T a b e l a 1

AND B C. D E. F. G. Temp. 15-60 60-80 80-90 90-95 95-100 100-103 103-106

H. J. K. L. M. N Temp. 106-110 110-115 115-125 125-140 140-160 160-FBP

Analyzes

A. Butan 9.1; isopentane 74.8; n-pentane 5.9; 2,3-dimethylbutane 5,6; 2-Methylpentane 1.8.

B. Isopentane 12.9; n-pentane 3.8; 2,3-dimethylpentane 20.7; 2-methylpentane 7.4; 3-methylpentane

3.8; 2,4-dimethylpentane 26.8; benzene 1; 2,3-dimethylpentane 12.2; isooctane 8.0.

C. Isopentane 2,3; 2,3-dimethylbutane 10.4; 2-methylpentane 3.8; 3-methylpentane 2,1; 2,4-dimethylpentane 23.4; 2,3-dimethylpentane 20.4; isooctane 31.5.

D. 2,3-Dimethylbutane 3,5; 2-methylpentane 1,3; 2,4-dimethylpentane 16.5; 2,3-dimethylpentane

19.9; isooctane 51.5.

PL 192 296 B1

E. 2,4-Dimethylpentane 7.2; 2,3-dimethylpentane 14.3; isooctane 67.1; 2,5-dimethylhexane 1,8;

2,4-dimethylhexane 2.0; 2,3,4-trimethylpentane 2,1; toluene 1.2; 2,3,3-trimethylpentane 1.0.

F. 2,4-Dimethylpentane 1,8; 2,3-dimethylpentane 7.5; isooctane 68.2; 2,5-dimethylhexane 4.1; 2,4-dimethylhexane 4.7; 2,3,4-trimethylpentane 6.0; toluene 1.4; 2,3,3-trimethylpentane 3.1; higher boiling 1.3.

G. 2,3-Dimethylpentane 4.5; isooctane 57.8; 2,5-dimethylhexane 6.0; 2,2,3-trimethylpentane 1,3;

2,4-dimethylhexane 7.0; 2,3,4-trimethylpentane 11.4; toluene 1.3; 2,3,3-trimethylpentane 6,3; higher boiling 3.0.

H. 2,3-dimethylpentane 1,3; isooctane 39.5; 2,5-dimethylhexane 7.9; 2,2,3-trimethylpentane 1,7;

2,4-dimethylhexane 9.2; 2,3,4-trimethylpentane 20.1; toluene 1.1; 2,3,3-trimethylpentane 12.1; higher boiling 6.9.

Isoparaffins n-Paraphms Aromas Other J. 92.0% C8 7.0% of Cg - 0.6% C7 K. 58.8% C8 38.8% Cg - 1.7% Ca L. 7.8% C8 72.8% of Cg 5.6% C10 - 11.8% Ca Total 1.9 M. 28.0% of Cg 46.5% C10 12.4% C11 Total 1.2 6.8% C8 4.9% of Cg - N 8.0% C10 37.5% C11 Total 1.2 1.2% C8 1.6% Cg A total of 49.9% higher boiling> C11

Examples 2 and 3

The base fuel was composed of 3.0 parts butane, 22.0 parts full range alkylate (used as feed in Example 1), 40 parts catalytic reforming product, 10 parts bisomer. 75 parts of this base fuel was combined with 25 parts of the J alkylate fraction providing the blend of Example 2, and also separately with 25 parts of the K alkylate fraction providing the blend of Example 3, and 25 parts of heavy reformer fraction providing the comparative blend.

3 prepared gasolines were produced, each of which contains one of the above mixtures and 15 mg / l of phenolic antioxidant, minimum 55% 2,4-dimethyl-6-tert-butylphenol, minimum 15% 4-methyl-2,6-tert-butylphenol, with the remainder being a mixture of monomethyl and dimethyl-tert-butylphenols. The gasolines of examples 2 and 3 meet the European guidelines of 2005 without using oxygenates.

In each case, gasoline was tested in terms of MON and RON and Reid's vapor pressure at 37.8 ° C. The results are shown in Table 2, which also shows the properties of the A-M alkylate fractions. The distillation properties of the blends of Examples 2 and 3 and the comparative blend were tested according to ASTM D86 and are shown in Table 3.

PL 192 296 B1

T a b e l a 2

Boiling point ° C RVP kPa RON MON Caloric value, Btu / lb Benzene% w / w Blend comparative 35-185 59.7 102.2 89.4 18339 1.86 Mixed ex. 2 34-172 57.2 99.6 89 18734 1.95 Mixed ex. 3 32-172 57.4 99.7 88.5 18733 1.94 Fraction A 15 to 60 - 90.8 87.8 19433 0.14 Fraction B 60 to 80 - 88.8 86.3 19088 1.07 Fraction C 80 to 90 - 91.2 89.7 19044 0.67 Fraction D 90 to 95 - 93.5 92.6 19010 0.33 Fraction E 95 to 100 - 95.5 94.8 18968 0.08 Fraction F 100 to 103 - 95.7 94.8 18935 0.01 Fraction G. 103 to 106 - 94.9 93.6 18958 0.00 H. Fraction 106 to 110 - 94.2 92.0 19010 0 Fraction J 110 to 115 - 91.8 87.8 19156 0.01 The K fraction 115 to 125 - 92.2 85.8 19157 0.01 Fraction L. 125 to 140 - - - 18949 0 M 140 to 160 - - - 18898 0 Fraction N 160 to FBP - - - 19005 0

T a b e l a 3

Blend comparative Example 2 Example 3 1 2 3 4 5 Initial boiling point ° C 34.7 34.2 31.6 deg C 05% sourced 56.4 57.9 57.1 deg C 10% harvested 68.6 68.7 68.6 deg C 20% harvested 87.4 84.4 85.1 deg C

PL 192 296 B1

continued table 3

1 2 3 4 5 30% sourced 101.8 94.7 96.0 deg C 40% sourced 113.8 101.5 103.5 deg C 50% harvested 124.9 107.1 109.3 deg C 60% harvested 135.5 111.6 114.1 deg C 70% harvested 145.1 116.1 118.8 deg C 80% sourced 154.5 122.1 124.8 deg C 90% sourced 165.0 137.8 137.5 deg C 95% sourced 173.9 155.4 154.2 deg C Final boiling point ° C 185.2 171.9 171.6 deg C Loss,% vol. 2.3 1.4 1.3 % vol. Recovery, vol.% 96.6 97.3 97.5 % vol. Residue,% vol. 1.1 1.3 1.2 % vol. Evaporation volume @ 70 ° C 12.7 11.9 11.9 - Evaporation volume @ 100 ° C 30.5 38.5 36.1 - Evaporation volume @ 150 ° C 77.1 94.9 95.2 - RVP kPa - 57.2 57.4 - Density kg / l - 0.7415 0.7423

P r z k ł a d 4

The characteristics of emissions during the combustion of prepared gasolines were compared: the comparative mixture, examples 2 and 3, and the A-N fractions.

The fuels were tested in a single-cylinder test engine at a load speed of 50 / 14.3 rpm. per min./Nm with a LAMBDA setting of 1.01 and the ignition timing has been optimized on the reference mixture. The emissions of CO, CO2, total hydrocarbons, NOX were measured for exhaust gases. The results were averaged. The results were as shown in Table 4 and are expressed as the change in emissions compared to the reference mixture and in addition the percentage change in gravimetric fuel consumption.

PL 192 296 B1

T a b e l a 4

Example WHAT CO2 C-H NOx Wear Comp. 0.0% 0.0% 0.0% 0.0% 0.0% 2 - 3.1% -4.1% - 4.0% - 3.7% - 2.3% 3 - 3.0% - 3.1% - 3.1% - 2.5% -2.1% AND - 38.6% - 10.8% - 33.1% - 11.3% - 7.2% B - 31.4% - 9.1% - 17.7% - 14.5% -6.1% C. -21.9% - 9.7% - 10.5% - 18.2% - 5.7% D - 18.4% - 8.9% - 8.1% - 19.3% - 5.3% E. - 9.4% - 9.2% - 4.0% -22.1% - 4.9% F. -4.1% - 9.3% - 1.7% - 22.2% - 4.8% G. - 5.1% - 9.7% 0.6% - 20.7% - 5.5% H. 2.0% - 9.3% 0.9% - 18.7%, - 5.0% J. - 3.0% - 9.0% - 5.0% - 18.0% - 5.4% K. - 3.2% - 9.2% 1.4% - 16.7% - 5.5% L. 0.2% -6.1% 3.0% - 15.0% - 3.6% M. - 3.5% - 7.2% 3.1% - 18.5% - 4.2% N - 1.3% - 4.8% 43.7% - 18.2% - 1.9%

As the test engines were not equipped with exhaust catalysts, the emission reduction is an indicator of the benefit of reducing the emissions upstream of the exhaust catalyst before the exhaust catalyst is warmed up and becomes effective; this corresponds to the cold start conditions.

Examples 5 and 6

Blends were prepared in the manner of Examples 2 and 3 from the base fuel (75 parts) and fraction A (25 parts) providing Example 5 and separately with pooled BE fractions (25 parts) to provide Example 6. The formulated gasolines were prepared as in Examples 2 and 3. They showed reduced emissions compared to the comparative mix.

P r z k ł a d 7

The blend was made of the following ingredients: steam cracked white spirit 32.0%, full range alkylate (as raw material in Example 1) 30%, A-E fraction 10%, reforming product 11.0%, toluene 16.0%, butane 1%. The formulated gasoline also contains 15 mg / L of the antioxidant from Example 2/3. The fuel properties are as shown in Table 5 below.

PL 192 296 B1

T a b e l a 5

RON 99.8 MON 87.9 Worth. caloric Btu / lb 18 616.0 S, ppm 7.3 RVP kPa 56.8 Benzene,% w / w 0.75 E70 ° C 18.9 E100 ° C 50.0 E150 ° C 93.5 E180 ° C 98.0 Aromas 34.2 Olefins 8.2 Saturated compounds 57.6 Oxygenates 0.0

This gasoline also produces reduced emissions.

Examples 8-11 and Comparative Example A

Various lead-free blends were prepared with each of the compounds A4, A6, A9, 2,2,5-trimethylhexane, in each case matching with different refinery streams as shown in Table 5, as well as a comparative example with heavy reformer.

In each case, the gasoline was tested for MON and RON and their Reid's vapor pressure at 37.8 ° C. The results are shown in Table 5 which also shows their analysis and distillation profile (according to ASTM D86).

The emission characteristics of prepared gasolines from Examples 8-11 and comparative mixture A.

The fuels were tested as in Example 4 in a single cylinder test engine at 20/7/2 rpm speed / load. per sec / Nm with LAMBDA setting 1.01 and with ignition setting optimized for reference mixture A. The exhaust emissions of CO, CO2, total carbon monoxide, total hydrocarbons, NOX and fuel consumption (expressed in g / hour ^{1) were measured} ). The results were averaged and compared to comparative example A. The degree of change is given in Table 6.

T a b e l a 6

Comp. AND 8 9 10 11 Fuel basic 1 2 3 4 5 6 Recipe% v / v Butane 3 3 3 3 3

PL 192 296 B1

continued table 6

1 2 3 4 5 6 Full range catalytically cracked white spirit twenty twenty twenty twenty twenty Alkylate 40 40 40 40 40 Light hydrocracked white spirit 7 7 7 7 7 Full-range steam cracked white spirit 10 10 10 10 10 Heavy reforming product twenty

2,2,5-Trimethylhexane (A17) twenty 2,2,4-Trimethylpentane (A4) twenty 2,3,3-Trimethylpentane (A6) twenty 2,3,4-Trimethylpentane (A9) twenty Density kg / l 0.7487 0.7159 0.7122 0.7192 0.7176 C: H. 1: 1,889 1: 2.085 1: 2.090 1: 2.091 1: 2.091 C% w / w 86.4 85.2 85.17 85.16 85.16 H% w / w 13.6 14.8 14.83 14.84 14.84 RON 97.0 96.6 97.8 97.1 MON 86.3 87.0 86.9 86.2 RVP kPa 54.7 57.1 56.1 56.1 T10% ° C 52.9 56.3 57.2 57.2 T50% ° C 107.0 93.6 97.7 97.4 T90% ° C 166.1 146.3 146.3 146.3 Benzene% v / v 0.6 0.6 0.6 0.6 0.6 Flavors% v / v 29.4 9.4 9.4 9.4 9.4 Olefins% v / v 9.0 9.0 9.0 9.0 9.0

PL 192 296 B1

Example WHAT CO2 COx Hydrocarbons NOx Saving fuel Comp. AND 0% 0.0% 0.0% 0.0% 0.0% 0.0% 10 11.8% - 2.8% - 2.4% -13.0% - 7.7% -1.4% 11 14.0% - 3.0% - 2.6% - 15.4% -4.1% -1.5% 8 21.9% - 2.8% - 2.2% - 9.0% - 4.6% 1.3% 9 14.0% - 4.4% - 4.0% - 14.4% - 4.8% - 1.8%

The data is the% change with respect to the base fuel (comparative fuel A).

Examples 12-23

The blends were made from the following ingredients: butane, full range boiling alkylate (used as a raw material in example 1), catalytic reformer product, light full range steam cracked white spirit, kerosene, crude gasoline, full range catalytically cracked white spirit, and 2,2,4- trimethyl pentane. In addition, most of the blends contained one or more of the alkylate fractions disclosed in Examples 2 and 3. Analyzes of the blends and their properties are shown in Table 7.

T a b e l a 7

Example 12 13 14 15 16 17 1 2 3 4 5 6 7 Butane 0.9900 1.8700 4.0900 2.6800 5.3700 5.6600 Full range alkylate 20.0000 20.0000 9.3500 10.0000 10.0000 10.0000 Product of catalytic reforming 16.7200 4.5000 12.8300 17.4400 21.1600 15.3800 Light hydrocracking product Full-range steam cracked white spirit 47.6900 53.6300 35.1000 42.5200 16.0500 20.0000 Oil 3.3900 0.7600 Raw gasoline 0.9700 Full range catalytically cracked white spirit 2.9300 2,2,4-Trimethylpentane 14.6000 20.0000 1.2600 Alkylate fraction 15 to 60 ° C Alkylate fraction 60 to 80 ° C Alkylate fraction 80 to 90 ° C

PL 192 296 B1

continued table 7

1 2 3 4 5 6 7 Alkylate fraction 90 to 95 ° C 38.6300 Alkylate fraction 95 to 100 ° C 27.3600 Alkylate fraction 100 to 103 ° C 42.7700 Alkylate fraction 103 to 106 ° C 44.3000 Alkylate fraction 106 to 110 ° C Alkylate fraction 110 to 115 ° C Alkylate fraction 115 to 125 ° C Properties RON 99.2000 99.1000 98.0000 98.8000 98.0000 98.0000 MON 87.0000 87.0000 87.0000 87.0000 88.4000 87.9000 RVP kPa 60.0000 60.0000 60.0000 60.0000 60.0000 60.0000 Evaporation @ 70 ° C% v / v 30,2000 32.4000 28.7000 28.2000 16.5000 16.3000 Evaporation @ 100 ° C% v / v 52.5000 56.5000 60.0000 54.4000 49.0000 49.0000 Evaporation @ 150 ° C% v / v 93.7000 94.8000 98.5000 96.3000 100.0000 99.8000 Evaporation @ 180 ° C% v / v 97.9000 98.0000 98.6000 98.2000 100.0000 99.8000 Density kg / l 0.7404 0.7301 0.7254 0.7376 0.726 0.7236 Benzene% v / v 1.0000 0.5100 0.7600 1.0000 1.0000 0.7800 Flavors% v / v 27.8000 22.2000 20.8000 26.4000 19.9000 17.9000 Olefins% v / v 12.4000 13.9000 9.1000 11.1000 4.7000 6.4000

The mixtures give reduced emissions during combustion.

T a b e l a 7 (cont.)

Example 18 19 twenty 21 22 23 1 2 3 4 5 6 7 Butane 4.5600 3.0300 4.0600 1.1300 Full range alkylate 17.5400 22.3500 19.9300 1.7600 5.2900 Product of catalytic reforming 8.5100 17.1800 12.1700 18.0600 21.0300 1.8100

PL 192 296 B1

continued table 7

1 2 3 4 5 6 7 Light hydrocracking product 19.7500 Full-range steam cracked white spirit 32.8500 30.2900 29.8000 38,1200 17.0000 26.1500 Oil 0.7900 Raw gasoline Full range catalytically grated white spirit 2.9800 2,2,4-Trimethylpentane Alkylate fraction 15 to 60 ° C 5.0000 12.3400 Alkylate fraction 60 to 80 ° C 5.0000 5.0000 Alkylate fraction 80 to 90 ° C Alkylate fraction 90 to 95 ° C 5.0000 5.0000 32.0000 Alkylate fraction 95 to 100 ° C 5.0000 5.0000 32.6900 39.1000 Alkylate fraction 100 to 103 ° C 5.0000 9.0400 Alkylate fraction 103 to 106 ° C 3.4400 2.1500 5.0000 Alkylate fraction 106 to 110 ° C 33.1000 Alkylate fraction 110 to 115 ° C 10.0000 15.0000 Alkylate fraction 115 to 125 ° C 10.0000 Properties RON 98.00000 98.0000 98.0000 98.7000 98.0000 98.0000 MON 87.0000 87.0000 87.0000 87.0000 87.9000 87.0000 RVP kPa 60.0000 60.0000 60.0000 60.0000 60.0000 60.0000 Evaporation @ 70 ° C% v / v 20.5000 22.6000 21.4000 30.4000 27.8000 22.1000 Evaporation @ 100 ° C% v / v 49.0000 49.0000 49.0000 59.3000 59.4000 54.4000 Evaporation @ 150 ° C% v / v 98.4000 96.4000 97.3000 98.0000 100.0000 99.7000 Evaporation @ 180 ° C% v / v 100.0000 99.2000 99.7000 98.5000 100.0000 99.8000 Density kg / l 0.7250 0.7310 0.7253 0.7334 0.7219 0.7295 Benzene% v / v 0.5600 0.9200 0.7000 1.0000 1.0000 1.0000 Flavors% v / v 17.2000 21.8000 18.5000 25.2000 20.3000 22.0000 Olefins% v / v 8.5000 7.9000 7.7000 9.9000 5.6000 6.8000

PL 192 296 B1

The mixtures give reduced emissions during combustion.

Examples 24-28

The blends were prepared from the following ingredients: butane, full boiling alkylate (used as a raw material in example 1), catalytic reforming product, full range steam cracked white spirit, kerosene. In addition, the blends contained one or more of the alkylate fractions disclosed in Examples 2 and 3. Analyzes of the blends and their properties are shown in Table 8.

T a b e l a 8

Example 24 25 26 27 28 1 2 3 4 5 6 Butane 0.1400 1.76000 Full range alkylate 37.7000 28.4700 17.1900 23.8100 Product of catalytic reforming 11,1200 12.6400 19.4000 8.9700 2.0300 Full-range steam cracked white spirit 23.5700 28:75 28.5900 24.1700 44.5600 Oil 13.0500 13.4100 Alkylate fraction 15 to 60 ° C 5.0000 5.0000 5.0000 Alkylate fraction 60 to 80 ° C 5.0000 5.0000 5.0000 5.0000 5.0000 Alkylate fraction 80 to 90 ° C 10.0000 10.0000 10.0000 Alkylate fraction 90 to 95 ° C Alkylate fraction 95 to 100 ° C Alkylate fraction 100 to 103 ° C Alkylate fraction 103 to 106 ° C Alkylate fraction 106 to 110 ° C Alkylate fraction 110 to 115 ° C 17.6100 15.0000 3.0600 5.0000 Alkylate fraction 115 to 125 ° C 5.0000 15.0000 15.0000 15.0000 Values RON 96.7000 96.9000 97.3000 93.0000 93.0000 MON 86.3000 85.8000 85.7000 83.0000 81.2000 RVP kPa 60.0000 60.0000 60.0000 52.8000 56.8000 Evaporation @ 70 ° C% v / v 24.1000 24.9000 22.9000 20.9000 30,2000 Evaporation @ 100 ° C% v / v 49.0000 49.0000 49.0000 49.0000 56.5000 Evaporation @ 150 ° C% v / v 95.5000 95.2000 95.3000 95.1000 95.3000

PL 192 296 B1

continued table 8

1 2 3 4 5 6 Evaporation @ 180 ° C% v / v 99.5000 100.0000 100.0000 100.0000 100.0000 Density kg / l 0.7200 0.7257 0.7336 0.7254 0.7293 Benzene% v / v 0.6200 0.7100 1.0000 0.5300 0.3500 Flavors% v / v 15.6000 18.4000 22.6000 15.6000 18.6000 Olefins% v / v 6.1000 7.5000 7.5000 6.3000 11.5000

The mixtures give reduced emissions during combustion.

Claims (4)

Patent claims A lead-free composition having a motor octane number MON of at least 80, characterized in that it comprises at least 10% by volume, based on the total composition, of component (a) (i) being a refinery-derived aliphatic hydrocarbon having a MON value of at least 85, wherein at least 70% of the total of this component is branched chain alkanes, which component is a mixture of different refinery fractions, each fraction obtained by distillation from the alkylate as a fraction with an initial boiling point of at least 15 ° C and a final boiling point of at most 160 ° C, and boiling points are measured according to ASTMD2892, and contains as component (g) at least 5% of at least one paraffinic, aromatic or olefinic hydrocarbon having a boiling point of 60-160 ° C, with the composition containing no more than 5% , relative to the total composition, a hydrocarbon with a boiling point above 160 °, less than 5% 2,2,3-trimethylbutane l or 2,2,3-trimethylpentane, and 2-40 vol.% aromatics. 2. A lead-free composition according to claim 1; 2. The method of claim 1, comprising 15-65%, in particular 20-35% by volume of component (a) (i). 3. Use of a lead-free composition as defined in Claim 1 for the production of upgraded unleaded gasoline containing at least one motor gasoline additive. 4. Use according to claim 1 A compound according to claim 3, characterized in that the lead-free composition comprises 15-65%, especially 20-35% by volume of component (a) (i).