WO2012023872A2

WO2012023872A2 - Synergistic compositions of anti-explosive additives for gasolines

Info

Publication number: WO2012023872A2
Application number: PCT/RO2011/000005
Authority: WO
Inventors: Constantin-Marius Vladulescu
Original assignee: Marine Resources Exploration International B.V.
Priority date: 2010-02-10
Filing date: 2011-02-08
Publication date: 2012-02-23
Also published as: RO127197A1; WO2012023872A3

Abstract

The invention refers to synergistic compositions of anti - explosive additives for gasolines. Compositions, according to the invention, are a mixture of components, including: an A component, which contains variable percentages of one or several aromatic amines, a B component containing variable percentages of aniline and Ν, Ν - dimethylaniline, a C component containing variable percentages of nitrobenzene and nitrotoluene isomers, anisole and optionally methylcyclopentadienyl manganese (II) tricarbonyl (MMT) and/or a metal deactivator.

Description

Synergistic compositions of anti-explosive additives for gasolines

This invention refers to the synergistic compositions of anti-explosive additives for gasolines used with spark ignition engines.

Anti-explosive additives are added to commercial gasolines to provide the minimum octane values required for the proper operation of modern spark engines, respectively the research octane number (RON) >95, and respectively the engine octane number (MON) >85, in compliance with the EC regulations provided by standard EN 228.

The first anti-explosive additives used in the industry were based on alkylate lead compounds. These additives are historical interest only, being eliminated due to their highly toxic features. Subsequently, other metal based additives were developed, such as those based on bis(dimethylcyclopentadienyl) Fe(ll) disclosed by patents GB226731 ; US4139349; WO0116257, and especially those of manganese methylcyclopentadienyl Mn(ll) tricarbonyl (MMT) disclosed by patents US4139349; EP046651 1 ; EP0476197. Generally, motor vehicle builders recommend avoiding additives with iron and manganese content because they affect the burnt gas conversion catalyst and also other engine elements, especially iron additives. Anti-explosive additives with manganese may be safely used especially in small enough concentrations (<18 mg Mn/L).

Simultaneously with the development of anti-explosive additives with iron and manganese content, the production and usage of additives belonging to the alcohol and ether class, generically defined as oxygenated additives, also developed. The t-butanol ethers are most frequently used: methyl-t-butyl ether (MTBE) (US4468233, US5752992) and ethyl-t-butyl ether (ETBE), as well as the ethanol derived from plants. Bioethanol must be added to gasolines at a 4% wt/wt concentration pursuant to EC regulations. Patent RU2005138060A describes the usage of phenol ethers: anisole and phenetole. The experimental verifications provided by the patent revealed an increase of 0.3 units relevant to a concentration of 1 % Wt/wt for a gasoline with initial RON 91.6. The disadvantage of these additives consists of their reduced capacity of increasing the octane number of gasolines; usually 0.22-0.25 units at a concentration of 1% wt/wt. Moreover, since the oxygen content of gasolines is limited to 2.6% by standard EN 228, the addition of oxygenated additives cannot exceed. As an alternative to the above mentioned anti-explosive additives we have aromatic amines, particularly N-methyl aniline. As described by the patents (GB252019; GB334181 A; GB530597; FR1255840; RU2184767; US2819953; US5470358; EP0235280; WO2008076759). Their efficiency is 4 - 15 times bigger than the efficiency of oxygenated compounds, however the costs are also 5 -10 times bigger. Moreover, their usage raises problems concerning some limitations as for the composites of the gasolines on the market.

The technical stage also comprises the use of nitroderivatives within the composition of anti-explosive additives. Therefore, patent RU2151169 C1 describes the preparation of some anti-explosive additives containing (% Wt wt) 0 - 6 nitrobenzene; 15-30 N-methylaniline; 0.5-5 aniline; 2 -5 N,N-dimethylaniline; the difference consisting of ethanol, butanol, isopentanol and MTBE. Patent CN1766068A mentions the use of an anti-explosive additive containing (% Wt wt): nitrobenzene 35 - 45 cyclohexanone 10-15 ; acetone 15-25; methoxi polyethylene 30-40.

Patent RO 121383 and patent application 2007 00776 describe the relevant procedures to obtain some synergistic compositions of anti-explosive additives.

The main disadvantages of the different types of anti-explosive additives and the multi-component systems compliant with the above mentioned documents, are as follows:

- Anti-explosive organometallic additives, especially in high concentrations, damage various engine parts; valves, spark plugs, catalytic converter and may pollute the environment;

- anti-explosive additives under the oxygenated compounds class require high concentrations in gasolines, usually 5 -16%, and the higher their concentration gets, the higher the emissions of volatile organic compounds and nitrogen oxides in combustion gases are;

- Anti-explosive additives under the aromatic amines class involve higher costs, and their higher concentrations may determine significant increases of the emissions of nitrogen oxides in the combustion gases, some of them being highly toxic.

The most effective solution, both technically and economically, regarding the gasoline additives, is based on additive mixtures from different classes, by favorably using the properties specific to each class and, as the case may be, the synergistic interactions between components.

The technical problem solved by this invention consists of eliminating the disadvantages of the existing solutions by obtaining some highly effective anti- explosion additives, whereas the components are selected and the compositions are formulated so as to reduce the additive dosages by making use of the synergistic interactions, and reducing the additive production cost.

The main disadvantages of the different types of anti-explosive additives and the multi-component systems formed by the above mentioned, are as follows:

Anti-explosive organometallic additives, especially in high concentrations, damage various engine parts; valves, spark plugs, catalytic converter and may pollute the environment.

Anti-explosive additives under the oxygenated compounds class require high concentrations in gasolines, usually 5 -16%, and the higher their concentration gets, the higher the emissions of volatile organic compounds and nitrogen oxides in combustion gases are.

Anti-explosive additives under the aromatic amines class involve higher costs and their higher concentrations may determine significant increases of the emissions of nitrogen oxides in the combustion gases, some of them being highly toxic.

The formulas are based on the experimental observations made by the author, which proved the existence of some synergistic interactions between the aromatic amines within component A and the aromatic amines within component B, the aromatic nitroderivatives within component C and the anisole and MT.

The invention extends the range of anti-explosive additives since it refers to synergistic compositions of anti-explosive additives for gasoline, characterized in that they constitute a mixture containing an A component, which contains one or several aromatic amines selected from: N-methylaniline, m-toluidine and p- toluidine, the concentration of the A component within the additive being at least 60% wt/wt, preferably 70-95% wt/wt, a B component, which contains various percentages of aniline and Ν,Ν-dimethylaniline, the concentration of the B component within the additive being 1 -20% wt wt, preferably 3-5% wt/wt, a C component which contains various percentages of nitrobenzene and nitrotoluene isomers, the C component concentration in the additive being 0-38% wt/wt, preferably 5-20%, anisoie with a concentration of 0-5% wt/wt in the additive, preferably 3% wt/wt, optionally, methylcyclopentadienyl manganese (II) tricarbonyl (MMT) with a maximum concentration of 12 mg/g in the additive, and optionally, a deactivator metal, such as N, N-disalicylidene-1 ,2 diaminopropane and antioxidant, under the antioxidant class, such as 2,6-di-t-butyl-p-cresol.

Table 1 features the characteristics of the A component constituents:

Table 1 Characteristics of the A component constituents

Table 3 features the characteristics of the C component constituents:

Table 3 Characteristics of the C component constituents

Table 4 features the characteristics of anisole and MMT

Table 4 Characteristics of anisole and MMT

The invention provides the following advantages:

a. optimizing the consumption of octane - booster additives, which also reduces the fuel consumption by 5 - 20% and determines efficiencies comparable to those provided by the individually used components.

b. reducing the additive cost by 5-15 %, and also the addition procedure costs c. possibility to obtain gasolines with high octane values RON > 100, compliant with standard EN 228

d. widens the range of anti-explosive synergistic compositions for the gasolines described by Patent RO 121383 and the patent application of 2007 00776

Bellow, we have 5 examples of how to prepare the compositions in compliance with this invention.

Example 1

Prepare by using the constituents presented in tables 1 , 2, 3 and 4, homogenizing by stirring, versions of the composition of component A (tab 5); B (tab 6), and respectively C (tab 7)

Table 5 Compositions of component A

Table 6 Compositions of component B

Table 7 Compositions of component C

These components, to which anisole is also added, are added according to a 2% wt/wt concentration to a gasoline with the characteristics presented in table 8.

Table 8 Composition of the gasoline subject to addition

RON and MON were measured on the samples of gasoline with additive content, according to standards SR EN ISO 5164:06; SR EN ISO 5183:06, and the obtained results are reference values (table 9). Table 9 Values of RON and ON

Mixture RON MON ARON ΔΜΟΝ

A1 96,2 84,1 4,4 2,7

A2 96,4 4,6

A3 96,1 4,3

A4 96,4 4,6

B1 96,1 4,3

B2 94,6 2,8

B3 96,4 83,9 4,6 2,5

C1 94,6 2,8

C2 95,2 84,1 3,4 2,7

C3 95,4 3,6

C4 95,4 3,6

C5 95,1 3,3

Anisole 92,5 0,7 0,4

By means of the formulated components A, B, C and (a) - anisole, the anti- explosive additives with synergistic properties are prepared in compliance with the description of this invention, marked AB1 -12; AB(a) 1 -4; ABC1 -4; AB(a)1 -4 with the compositions in tables 10 -14.

Table 11 Composition of additives AB5 - AB8

mixtures additive compositions % wt/wt additive N- N,N-

A2 B3 methylaniline aniline dimethylaniline

AB5 98 2 98 1 ,6 0,4

AB6 96 4 96 3,2 0,8

AB7 94 6 94 4,8 1 ,2

AB8 90 10 90 8 2

The additives with the respective compositions were dosed 2% wt wt in the gasoline with the composition from table 8 and then, the RON values of the additivated gasoline were determined according to standard SR EN ISO 5164:06, the results are provided In table 15. The mixtures express synergistic interactions in all situations. The synergistic effect:

ASp_Q where [X] = [RON] or [MON] was calculated by means of the relation:

where X = the measured value RON or MON of the additive formed by mixtures Pi ; being the mass percentage of each component and X, = the measured value of RON and MON for each mixture 1....Ϊ, in the same gasoline and in the same concentration as the additive formed by the respective mixtures.

Table 15

Determining the anti-explosive effect of the

additives in tables 10 - 14

AB(a) 1 96,7 4,9 4,2 0,7

AB(a)2 96,6 4,8 4,1 0,7

AB(a)3 97,1 5,3 4,1 1 ,2

AC(a)4 96,6 4,8 4,0 0,8

Example 2

The additive marked ABC 5 is prepared in compliance with the description of this invention, with the following composition:

The gasoline is additivated with the composition from table 8, example 1 , in different concentrations (%wt/wt ) with the additive ABC5 and comparable with N- methylaniline and MTBE. The RON values of the additivated gasoline were measured according to standard SR EN ISO 5164:06. The resulted values relevant to the increase of the octane number RON; ARON are presented in fig.1 and fig. 2. The experimental data is used for the calculation of the following additive dosages in view of obtaining the gasoline on the market with RON = 95.2:

Fig. 1 Variation of the octane number ARON

^depending on the C additive concentration (% wt/wt);

0,5 1 1 ,5 2,5 additive concentration % wt/wt

By using the relative average prices, reported to the price of non-additivated gasoline:

and considering the additive dosages, we obtain the following relative costs for the additivated gasoline up to RON 95.2

Example 3

In compliance with this invention, the anti-explosive additive named ABC(a)1 is prepared with the composition (%Wt/wt ):

*N,N-disalicylidene-1 ,2-diaminopropane

** 2,6-di-t-butyl-p-cresol, added in variable dosages to the gasoline with the composition: %

component wt/wt

gasoline cracking 52,4

gasoline reforming 42,5

other fractions 5,1

octane numbers

RON 94,3

MON 82,4

For comparison, the same gasoline was also additivated with N- methylaniline. The results of the RON measurement, pursuant to SR EN ISO 5164:06, are illustrated in fig. 3. The use of additive ABC 5, in a dose of 0.75% wt/wt in the gasoline in this example, allows us to obtain a 95 type commercial gasoline compliant with standard EN 229, and its composition is presented bellow:

Fig. 3 Comparative additivation curve between

additive ABC (a) 1 and N -methylaniline and

additive concentration % wt/wt

5 1 1.5 2

additive concentration % wt/wt Characteristic MU value Analysis standard density 15C kg/m³ 741 SR EN ISO 3675:03

RO 95,4 SR EN ISO 5164:06

MON 85,2 SR EN ISO 5183:06 sulphur content mg/kg 7,0 SR EN ISO 20846:04 evaporation at 100C % v/v 61 ,2 SR EN ISO 3405:03 final boiling point C 201 SR EN ISO 3405:03 distillation residue % v/v 1 ,2 SR EN ISO 3405:03 actual gums mg/100mL 1 ,3 SR EN ISO 6246:00

Example 4

In compliance with this invention, the anti-explosive additive ABC prepared:

** 2,6-di-t-butyl-p-cresol,

which was added in a dose of 3% wt/wt in a gasoline with the following characteristics:

resulting an additivated gasoline with RON > 101 , with characteristics compliant to standard EN 228:

Claims

1. Synergistic compositions of anti-explosive additives for gasolines characterized in that they consist of a mixture containing:

- an A component, which contains one or several aromatic amines selected from: N-methylaniline, m-toluidine and p-toluidine, the concentration of the A component within the additive being at least 60% wt/wt;

- a B component, which contains various percentages of aniline and N,N- dimethylaniline, the concentration of the B component within the additive being 1 -20% wt/wt;

- a C component, which contains various percentages of nitrobenzene and nitrotoluene isomers, the C component concentration in the additive being 0-38% wt/wt;

- anisole with a concentration of 0-5% wt/wt in the additive;

- optionally, methylcyclopentadienyl manganese (II) tricarbonyl (MMT) with a maximum concentration of 12 mg/g in the additive, and

- optionally, a deactivator metal, such as N, N-disalicylidene-1 ,2 diaminopropane and antioxidant, under the antioxidant class, such as 2,6- di-t-butyl-p-cresol.

2. Synergistic compositions according to claim 1 characterized in that the concentration of component A in the additive is preferably 70-95% wt/wt.

3. Synergistic compositions according to claim 1 characterized in that the concentration of component B in the additive is preferably 3-5% wt/wt.

4. Synergistic compositions according to claim 1 characterized in that the concentration of component C in the additive is preferably 5-20% mm.

5. Synergistic compositions according to claim 1 characterized in that the concentration of anisole in the additive is preferably 3% wt/wt. References:

CN1766068A

EP0235280

FR1255840

GB252019

GB334181A

GB530597

RU2005138060A

RU2151 169 C1

RU2184767

US2819953

US5470358

US5752992

WO2008076759

RO 121383 a 2007 00776