BR112017027947B1 - IMPROVED OCTANE NUMBER GASOLINE COMPOSITIONS - Google Patents

Abstract

IMPROVED OCTANE NUMBER GASOLINE COMPOSITIONS. The present invention is directed to a new gasoline composition comprising a gasoline fuel and from 0.05 to 1% of a low specific amount of a glycerol ketal or acetal. The new gasoline composition shows a higher octane number compared to known gasoline compositions. The invention also relates to the use of said glycerol ketal or acetal as an octane-free metal boosting additive for the octane adjustment of gasoline compositions.

Description

FIELD OF THE INVENTION

The present invention relates to a new gasoline composition containing a specific amount of glycerol ketal or acetal as an additive capable of boosting the octane number of the gasoline composition. The invention also relates to the use of said glycerol ketal or acetal as an octane-free metal boosting additive for the octane adjustment of gasoline compositions.

BACKGROUND OF THE INVENTION

Gasoline, also known as "petrol" outside North America, is a clear liquid derived from petroleum that is primarily used as a fuel in internal combustion engines. It consists mainly of organic compounds obtained by the fractional distillation of petroleum, enhanced with a variety of additives.

Spark ignition engines are designed to burn gasoline in a controlled process called deflagration. However, the unburned mixture can self-ignite through separate pressure and heat detonation, rather than igniting from the spark plug at exactly the right time. This causes a rapid increase in pressure that can damage the engine. This is often called an engine knock or end-gas pin knock. Knocking can be reduced by increasing the gasoline's resistance to auto-ignition, which is expressed by its octane number.

In fact, the characteristic of a specific gasoline blend to resist ignition too early (which causes knocking and reduced efficiency in reciprocating engines) is measured by its octane number. Gasoline is produced in varying degrees of octane numbers (octane).

The octane number is measured relative to a mixture of 2,2,4-trimethylpentane (an isomer of octane) and n-heptane. The second has an octane number of 0, while that of isooctane (2,2,4-trimethyl pentane) is 100. Linear combinations of these two components are used to measure the octane number of a specific fuel. A 90%/10% iso-octane/n-heptane blend has an octane value of 90. Any fuel that hits the same compression ratio as this blend is said to have an octane rating of 90.

There are different conventions for expressing octane numbers, so the same physical fuel can have several different octane ratings based on the gauge used. One of the best known is the lookup octane number (RON).

Research octane number (RON) is measured under mild conditions (inlet temperature and RPM), indicative of normal road performance, while engine octane number (MON) is measured under severe conditions (inlet temperature and RPM). ), indicative of high-speed performance. The spread between the two numbers (MON & RON) is known as the fuel sensitivity. Classically, both numbers are measured with a variable compression ratio engine and a standardized single cylinder. For RON and MON, the engine is operated at a constant speed (RPM) and the compression ratio increases until the start of its beat. For RON the motor speed is set at 600 rpm and for MON it is at 900 rpm.

Gasoline is produced in oil refineries from crude oil.

Most typical gasoline consists of hydrocarbons with between 4 and 12 carbon atoms per molecule (commonly called C4-C12). It is a mixture of paraffins (alkanes), cycloalkanes (naphthenes) and olefins (alkenes), where the use of the terms paraffin and olefin is particular to the petroleum industry. The actual rate depends on: - the oil refinery that manufactures the gasoline, as not all refineries have the same set of processing units; - the crude oil feed used by the refinery; - the grade of gasoline, in particular the octane rating.

The various refinery streams blended together to produce gasoline have different characteristics. Some important streams are: - Direct-distilled gasoline, commonly called naphtha, is distilled directly from crude oil. Once the main fuel source, its low octane rating required lead additives. It is low in aromatics (depending on the grade of crude oil), containing some cycloalkanes (naphthenes) and no olefins (alkenes). Between 0 and 20% of this stream is grouped in the finished gasoline. - the reformate, produced in a catalytic reformer, has a high octane rating with a high aromatic content and relatively low olefin (alkene) content. Most benzene, toluene and xylene (so called BTX) are more valuable as chemical feedstocks and therefore are removed to some extent. - catalytic cracked gasoline or catalytic cracked naphtha, produced from a catalytic cracker, with moderate octane number, high olefin (alkene) content and moderate level of aromatics. - hydrocracked (heavy, medium and light) produced from a hydrocracker, with a medium to low octane rating and moderate aromatic levels. - The alkylate is produced in an alkylation unit, using isobutane and alkenes as raw materials. The alkylate does not contain aromatics and the alkenes have a high MON. - The isomer is obtained by isomerization of low-octane direct-distilled gasoline to isoparaffins (without alkane chain, such as iso-octane). The isomer has medium RON and MON, but no aromatics and olefins. - butane is generally mixed in the gasoline pool, although the amount of this flow is limited by Reid's Vapor Pressure specification; which regulates the volatility of gasoline.

The above terms are jargon used in the oil industry and terminology varies.

Gasoline can also contain other organic compounds, such as (deliberately added) organic ethers, as well as small levels of contaminants, in particular organosulfur compounds, but these are usually removed at the refinery.

Gasoline generally also comprises various additives such as: - Alcohols: Methanol, ethanol, isopropyl alcohol, n-butanol, gasoline grade t-butanol; - Ethers: tert-butyl methyl ether (MTBE), now banned in many US states for road use, primarily because of water contamination, tertiary amyl methyl ether (TAME), tertiary methyl hexyl ether (TEMA), tertiary ethyl butyl ether (ETBE) Tertiary amyl ethyl ether (TAEE), diisopropyl ether (DIPE); - Antioxidants, stabilizers: Butylated hydroxytoluene (BHT), 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butylphenol (2,6-DTBP), p-phenylendiamine, ethylene diamine; - Antiknock agents: Tetraethyllead, Methylcyclopentadienyl manganese tricarbonyl (MMT), Ferrocene, Iron pentacarbonyl, Toluene, Iso-octane, Triptan - Lead scavengers (for leaded gasoline): Tricresyl phosphate (TCP), 1,2-Dibromoethane, 1,2-Dichloroethane; - Most common fuel dyes: Solvent Red 24, Solvent Red 26, Solvent Yellow 124, Solvent Blue 35.

Tetraethyl lead and other lead compounds are no longer used in most areas to regulate and increase the octane rating due to health and environmental concerns.

Methylcyclopentadienyl manganese tricarbonyl (MMT) is used in Canada and Australia to increase octane, but its use in the US has been restricted by regulations.

US4390345 describes the use of 1,3-dioxolane and its lower alkyl or alkenyl derivatives as exhaust hydrocarbon emission reducers for gasoline compositions containing MMT pin antiknock. As explained earlier, the use of MMT containing gasoline compositions is now restricted due to their toxicity to the environment.

EP2298851 describes the use of a mixture of alcohol and cyclic ketal with at least 10% by weight of the gasoline composition in order to improve the octane number of the composition. It is also specified that the use of 10% by weight of a cyclic ketal of glycerol-acetone in gasoline increases the octane number by 1.4 units.

There are several units at the refinery that are completing the recycling and upgrading of naphtha into components that end up in the refinery's gasoline blending/pooling facilities, including high and low octane components that are blended to produce a commercial grade gasoline with the desired octane.

In the mixing process, all specification parameters need to be met, such as distillation curves and Octane Numbers. There are two (2) types of octane improvers: - Blending Components: They are used in high percentages, usually around 10-20% in the blending process. For example, MTBE (under review for toxicity) and Ethanol; - Octane Boosting Additives: They are used to increase the Octane Number of final blends.

Generally 2000 to 10000 ppm maximum to meet the desired RON number.

It is difficult to mix the gasoline, find all the technical parameters and always find the final octane target, because most of the calculations are done by computer simulations and most of the mixing is done in large quantities with operating volume losses in loads or pipelines. For example, you can finish a blend of a gasoline with an expected RON of 98 with all the correct specs and when you do the final sample tests (top, middle and bottom of the storage tank), your average RON is at 97.8. In this case, you must add Octane boosters that are mixed in the tank in an operation of less than 12 hours. Currently, the main technologies are metals, Manganese (MMT) or iron (ferrocene), for example. These technologies are under much scrutiny due to emission effects.

One of the objects of the invention is to propose an improved metal-free, high octane number gasoline composition with reduced emission impact during combustion.

Another object of the invention is to provide a metal-free, non-toxic octane boosting additive for adjusting the octane of gasoline compositions that is effective at low dosage.

Another object of the present invention is to propose a non-toxic metal-free octane boosting additive for the octane adjustment of gasoline compositions that is at least partially sourced from bioresources.

SUMMARY OF THE INVENTION

em queThe invention thus proposes a metal-free gasoline composition comprising at least one gasoline fuel and from 0.05 to 1% by weight of an octane boosting additive comprising at least one compound of formula I below:

on what

R1 and R2, independently of one another, are selected from the group consisting of: a linear or branched C1-C12 alkyl, a C4-C12 cycloalkyl or an aryl.

R3 is H, a linear or branched alkyl, a cycloalkyl or a -C(=O)R4 group, with R4 being a linear or branched C1-C4 alkyl or a C5-C6 cycloalkyl.

The present invention also proposes the use of 0.05 to 1% by weight of a composition comprising at least one compound of formula I described above according to all possible embodiments and combinations thereof as an octane boosting additive for a composition of Gasoline. In particular, use is as an octane boosting additive to adjust the octane number of a blended gasoline fuel.

DETAILED DESCRIPTION OF THE INVENTION

em que R1 e R2, independentemente um do outro, são selecionados a partir do grupo que consiste em: uma C1-C12 alquila linear ou ramificada, uma C4-C12 cicloalquila ou uma arila. R3 é H, uma alquila linear ou ramificada, uma cicloalquila ou um grupo -C(=O)R4, com R4 sendo uma C1-C4 alquila linear ou ramificada ou uma C5-C6 cicloalquila.The metal-free gasoline composition of the invention comprises at least one gasoline fuel of 0.05 to 1% by weight of an octane boosting additive comprising at least one compound of formula I below:

wherein R1 and R2, independently of one another, are selected from the group consisting of: a linear or branched C1-C12 alkyl, a C4-C12 cycloalkyl or an aryl. R3 is H, a linear or branched alkyl, a cycloalkyl or a -C(=O)R4 group, with R4 being a linear or branched C1-C4 alkyl or a C5-C6 cycloalkyl.

In a preferred embodiment, R3 and R2, independently of one another, are selected from the group consisting of: methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n-pentyl, cyclopentyl, cyclohexyl or phenyl.

Advantageously, in formula I above R3 is H or a -C(=O)R4 group, with R4 being methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl or tert-butyl.

A preferred embodiment is when R1 and R2 are methyl and R3 is H. In this case, the compound is commercially available, for example under the name Augeo® Clean Multi, Augeo® SL191 or Solketal. This compound can be synthesized by reaction between glycerol and acetone, under well-known classical conditions.

In another embodiment, R1 is methyl, R2 is isobutyl and R3 is H. In this case, the compound is commercially available, for example under the name Augeo® Clean Plus. This compound can be synthesized by reaction between glycerol and methyl isobutyl ketone, under well-known classical conditions.

In a third embodiment, R1 is methyl, R2 is phenyl and R3 is H. In this case, the compound is commercially available, for example under the name Augeo® Film HB. This compound can be synthesized by reaction between glycerol and acetophenone, under well-known classical conditions.

Another possibility is to have R1 and R2 being methyl and R3 being a -C(=O)R4 group, with R4 being methyl. In this case, the compound is commercially available, for example under the name Augeo® ACT. This compound can be synthesized by transesterification of Solketal with an alkyl acetate, under well-known classical conditions.

Glycerol can be obtained as a co-product of biodiesel production during the transesterification of triglycerides. Glycerol is therefore a product that can come from bioresources.

Usual octane boosting compounds are not environment friendly: Lead additives are catalytic converting catalysts of poison and toxic air pollutants. In Gasoline, benzene is a carcinogen, aromatics produce more smoke and smog, and olefins form engine scale gums, more smoke and smog.

The formula I compounds of the invention have very good application performance, low odor and no toxicity to humans or the environment. Furthermore, its use does not induce safety issues due to its high flash point. They are sustainable alternatives to existing octane boosters in gasoline application, as they meet the three pillars of sustainability (economic, environmental and social).

It is also a favorable embodiment when a mixture of two or more compounds of formula I is used in the gasoline composition according to the invention. This mixture preferably comprises Augeo® Clean Multi and Augeo® Clean Plus, in a weight ratio of from about 30:70 to 70:30, and even more preferably, from 50:50. Another advantageous mixture comprises Augeo® Clean Plus and Augeo® ACT, in a weight ratio of 30:70 to 70:30, and even more preferably, 60:40.

One possible embodiment is when the octane boosting additive consists of one or more compounds of formula I.

Furthermore, the gasoline octane booster additive according to the invention may further comprise esters of C1-C6 carboxylic acids and/or ketones such as butyl acetate, propyl acetate, Methyl Isobutyl Ketone and Methyl Ethyl Ketone, advantageously ethyl. According to this embodiment, the molar ratio of the compound of formula I/esters of C1-C6 carboxylic acids and/or ketones and, in particular, the molar ratio of the compound of formula I/ethyl acetate can be from 30:70 to 100:0, preferably from 50:50 to 95:5.

In summary, according to the invention "from 0.05 to 1% by weight of an octane booster additive comprising at least one compound of formula I" means that the octane booster can be 100% of at least one compound of formula I or may comprise a minimum of 0.015% of at least one compound of formula I, the rest being esters of C1-C6 carboxylic acids and/or ketones such as butyl acetate, propyl acetate, Methyl Isobutyl Ketone and Methyl Ethyl Ketone, advantageously ethyl acetate.

In the gasoline composition according to the invention, it is particularly preferred that the octane booster additive is present in an amount of from 0.1 to 1.0%, preferably from 0.2 to 1% and even more preferably, from 0.2 to 0.8% by weight of the total weight of the gasoline composition.

The gasoline fuel may comprise a complex mixture of light hydrocarbons containing 5-12 carbon atoms produced in petroleum refineries. Gasoline is composed of more than 200 chemicals, such as: benzene (up to 5%), toluene (up to 20%), naphthalene (up to 2%), trimethylbenzene (up to 5%) and others.

The present invention also proposes the use of 0.05 to 1% by weight of a composition comprising at least one compound of formula I described above according to all possible embodiments and combinations thereof as an octane boosting additive for a composition of Gasoline. In particular, use is as an octane boosting additive to adjust the octane number of a blended gasoline fuel.

All the specific embodiments described above for the composition of gasoline also apply to the above mentioned use.

The introduction of the compound of formula I above into gasoline leads to gasoline engine fuels, allowing to increase the octane number with respect to a fuel that does not contain the products in question. For example, the invention surprisingly, with a dose as low as 1% Augeo SL191, allows for an increase in octane number of 0.6, which is well above prior art expectations.

The following examples illustrate the invention in a non-limiting form.

DESCRIPTION OF THE FIGURES

Figures 1 to 3 correspond to the octane number measurement diagrams (RON and MON) as a function of the amount of Augeo® SL191 added for three different gasoline fuels. These numbers relate to examples 1 to 3.

Figures 4 and 5 are diagrams of octane measurement (RON and MON) as a function of the amount of Augeo® SL191 and ethyl acetate added to two different gasoline fuels as described in Examples 4 and 5.

EXAMPLES measurement methods

Tabela I - métodos de mediçãoFor the examples below, the parameters were measured according to the standards indicated in Table I below.

Table I - measurement methods

Tests and results

The octane number results (RON and MON) were measured for different types of gasoline, after the addition of different additives, followed by a reasonable stirring time (approximately 10 minutes). The results are as shown in examples 1 to 5 below.

Example 1: RON 95 Gasoline (Oxy-Free Unleaded) - Augeo® SL191

This type of gasoline is suitable for high performance cars because its minimum specification of RON is 95. Availability will depend on the needs and habits of each region, but it is quite common in Europe and some Latin American countries, for example.

Tabela IIAugeo SL191, which is commercially available, was added at the concentrations indicated below and the octane numbers were measured according to the aforementioned standard. Table II below indicates the results obtained.

Table II

The diagram for this example is shown in Fig. 1.

Example 2: 91 unleaded gasoline - Augeo® SL191

Gasoline which, despite the minimum RON of 91 as a specification, also does not require a lead content. Availability will depend on the needs and habits of each region, but it is quite common in Australia and New Zealand, for example.

Tabela IIIAugeo SL191, which is commercially available, was added at the concentrations indicated below and the octane numbers were measured according to the aforementioned standard. Table III below indicates the results obtained.

Table III

The diagram for this example is shown in Fig. 2.

Example 3: SP95 - Augeo® SL191

SP95 stands for "sans plomb", which in French means unleaded, and 95 is the minimum required RON. Availability depends on the needs and habits of each region, but it is quite common in Europe, for example.

Tabela IVAugeo SL191, which is commercially available, was added at the concentrations indicated below and the octane numbers were measured according to the aforementioned standard. Table IV below indicates the results obtained.

Table IV

The diagram for this example is shown in Fig. 3.

Example 4: Gasoline 91 - Augeo® SL191 and ethyl acetate

Tabela VA mixture of 50% by weight of Augeo SL191 and 50% of ethyl acetate, both commercially available, was prepared and then added at the concentrations indicated below and the octane numbers were measured according to the aforementioned standard. Table V below indicates the results obtained.

Table V

The diagram for this example is shown in Fig. 4.

Example 5: SP95 - Augeo® SL191 and ethyl acetate

Tabela VIA mixture of 50% by weight of Augeo SL191 and 50% by weight of ethyl acetate, both commercially available, was prepared and then added at the concentrations indicated below and the octane numbers were measured according to the aforementioned standard. Table VI below indicates the results obtained.

Table VI

The diagram for this example is shown in Fig. 5.

Comparative example: Unleaded alcohol-free gasoline-Augeo® SL191 at 1.45%

Tabela VIIAugeo® SL191, which is commercially available, was added at the concentrations indicated below and the octane numbers were measured according to the aforementioned standard. Table VII below indicates the results obtained.

Table VII

The above results show that at a very low dosage of the Formula I components by themselves or as a mixture with esters they are able to improve the octane number of different types of gasoline, and both the RON and MON parameters. On the contrary, by adding a larger amount of Augeo SL191 (see comparative example) to the gasoline, the octane boosting effect disappears.

Claims (10)

1. A metal-free gasoline composition, characterized in that it comprises at least one gasoline fuel and from 0.05 to 1% by weight, based on the total weight of the metal-free gasoline composition, of an octane-enhancing additive consisting of at least one compound of formula I below:

wherein R1 and R2, independently of one another, are selected from the group consisting of: a linear or branched C1-C12 alkyl, a C4-C12 cycloalkyl or an aryl. R3 is H or a -C(=O)R4 group, with R4 being a straight or branched C1-C4 alkyl or a C5-C6 cycloalkyl; and at least one C1-C6 carboxylic acid ester and/or ketone, preferably ethyl acetate; wherein the molar ratio of the compound of formula I/C1-C6 carboxylic acid esters and/or ketones is from 50:50 to 95:5. 2. Composition of gasoline, according to claim 1, characterized in that R1 and R2, independently of each other, are selected from the group consisting of: methyl, ethyl, isopropyl, n-propyl, isobutyl, n - butyl, tert-butyl, n-pentyl, cyclopentyl, cyclohexyl or phenyl. 3. Composition of gasoline, according to claim 1 or 2, characterized in that R3 is H or a group - C(=O)R4, where R4 is methyl, ethyl, isopropyl, n-propyl, isobutyl, n- butyl or tert-butyl. 4. Composition of gasoline, according to any one of claims 1 to 3, characterized in that R1 and R2 are methyl and R3 is H. 5. Gasoline composition, according to any one of claims 1 to 3, characterized in that R1 is methyl, R2 is isobutyl and R3 is H. 6. Gasoline composition according to any one of claims 1 to 3, characterized in that R1 is methyl, R2 is isobutyl and R3 is H. 7. Gasoline composition according to any one of claims 1 to 3, characterized in that R1 and R2 are methyl and R3 is a -C(=O)R4 group, with R4 being methyl. A gasoline composition according to any one of claims 1 to 7, characterized in that it comprises a mixture of two or more compounds of formula I. 9. Composition of gasoline, according to any one of claims 1 to 8, characterized in that the octane booster additive is present in an amount of 0.1 to 1.0%, preferably from 0.2 to 1 % and even more preferably from 0.2 to 0.8% by weight of the total weight of the gasoline composition. 10. Use, characterized in that it is 0.05 to 1% by weight, based on the total weight of the metal-free gasoline composition, of an octane boosting additive consisting of at least one compound of formula I below:

wherein R1 and R2, independently of one another, are selected from the group consisting of: a linear or branched C1-C12 alkyl, a C4-C12 cycloalkyl or an aryl. R3 is H or a -C(=O)R4 group, with R4 being a straight or branched alkyl or cycloalkyl; and at least one C1-C6 carboxylic acid ester and/or ketone, preferably ethyl acetate, wherein the molar ratio of the compound of formula I/C1-C6 carboxylic acid esters and/or ketones is 50:50 to 95:5, as an octane number boosting additive for a gasoline composition.

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