WO2014178810A2

WO2014178810A2 - Motor fuel

Info

Publication number: WO2014178810A2
Application number: PCT/UA2013/000110
Authority: WO
Inventors: Vladislav BORYSHCHUK; Viktor GORBACH; Zaur TSINTSADZE; Ievgen POLUNKIN; Georgy MSHVENIERADZE; Olha GAIDAI
Original assignee: Boryshchuk Vladislav; Gorbach Viktor; Tsintsadze Zaur; Polunkin Ievgen; Mshvenieradze Georgy
Priority date: 2013-04-30
Filing date: 2013-09-24
Publication date: 2014-11-06

Description

MOTOR FUEL

The invention relates to field of oil refining and petrochemistry, namely the development and manufacturing of composite motor fuel with useful additives that determine improved energy, environmental and tribological characteristics of the fuel.

The effective additives to gasoline are oxygenates - oxygen-containing compounds, which improve anti-knock performance and reduce the content of harmful compounds in exhaust emissions. The most known and permitted for using in Ukraine is the "High octane oxygen-containing additive" based on absolute ethanol, or with another title - "The component of alternative motor fuel". It refers to already developed motor fuels with relatively high ethanol content. Increasing the amount of ethanol not only raises the octane rating of the fuel, but also saves valuable non-renewable hydrocarbon components, makes it possible to reduce the content of high- toxic aromatic compounds in gasoline, and also extends the raw material base for the fuel production at the expense of using of renewable biological resources.

However, the decreasing in the content of natural oil components, which contain sulfur and condensed aromatic compounds, leads to deterioration in lubricating performance of fuels mentioned above.

Currently in use the blended fuel composition [1], which is used in spark-ignition engines and both includes gasoline and bioethanol motor fuel as the oxygenate component with additives, in which the halogenated fullerenes involved.

The drawback of this blended fuel composition is insufficiently high antifriction properties. Additionally chlorine containing fullerenes at slightly lower combustion temperatures, generated during combustion of fuels with a high content of oxygenates, promote the formation of highly toxic and environmentally hazardous dioxins.

Currently in use the alternative fuel for spark-ignition engines [2] which includes bioethanol and a hydrocarbon solvent.

The drawback of this alternative fuel is the using of acetone, ethyl cellosolve and butyl cellosolve as stabilizers, which are quite aggressive solvents and corrosive compounds, as well as harmful to health (risk class III).

The most similar to the claimed invention is a motor bioethanol fuel [3], which comprises as main components, % wt.:

- Aromatic amines - 0.05-1.00;

- Stabilizer - 0.01 - 3.00;

- Hydrocarbon fraction (overpoint - 60 ° C) - 0.01- 10.00;

- Halogenated fullerenes - 0.0001 - 0.5000;

- Bioethanol - rest.

The drawback of this bioethanol motor fuel is unsatisfactory environmental and tribological fuel characteristics.

In the basis of the invention "Motor fuel" the developing of alternative motor fuel with a system of improved performance characteristics - namely, increased anti-knock resistance, low emissions and improved tribological properties had been tasked.

The assigned task solves by the use of motor fuel containing liquid fuel and additive; in the capacity of additive is used the solvatosol of carbon nanosized spherical clusters CNOs to the extent from 1 to 500 nm; these clusters consist of laminated partially closed cockleshell-like form graphene layers, and additionally in the capacity of substituents contain the functional groups, notably amino groups and heterocyclic bases including oxygen, hydrogen, nitrogen to the extent from 1 to 700 atoms in the following ratio of components, wt. %:

Liquid fuel - 90,5 - 99,999;

Additive - 0,001 - 9,5.

In the capacity of liquid fuel is used a mixture of hydrocarbon fuel and motor bioethanol fuel in the following ratio of components, wt. %:

- Hydrocarbon fuel - 0,001 - 99,999;

- Motor bioethanol fuel - 0,001 - 99,999.

The carbon nanosized spherical clusters consisting of laminated partially closed cockleshell-like form graphene layers contain endohedral atoms including rare earth, transition and heavy metals (Chromium, Manganese, Iron, Lanthanum, Nickel, Cobalt).

Character of the invention. The introduction of solvatosol of spherical carbon nano clusters CNOs into additive leads to the formation of supramolecular structures of micellar type - domains, which consist of nanoparticle and a solvent molecule. Domains change the mechanism of contact between two surfaces which interact, and thus prevent the contact of metals on the surfaces of friction and improve the tribological characteristics.

In addition, the technical result is ensured that as the additive for motor fuels acts solvatosol of spherical carbon nano clusters CNOs to the extent from 1 to 500 nm. These clusters consist of laminated partially closed cockleshell-like graphene layers, and additionally in the capacity of substituents contain functional groups (amino groups, heterocyclic bases) with halogens (F, CI, Br), oxygen, hydrogen, nitrogen to the extent from 1 to 700 atoms.

In the capacity of liquid fuel the motor fuel contains hydrocarbon fuel and bioethanol fuel and mixtures thereof in the claimed amount which is optimal.

A characteristic feature of the of spherical nano clusters CNOs is that they contain endohedral inclusions of metal atoms (Cr, Mn, Fe, La, Ni, Co). Introduction into the fuel composition of microquantities of these compounds allows changing significantly such a physicochemical characteristics of the fuel as density, refractive index, viscosity, ability to oxidize and tribological characteristics.

Motor fuel was prepared as follows. Claimed motor fuel is produced by compounding of components by adding an additive in the manufactured liquid fuel in a predetermined amount. Motor fuel is produced by compounding of the preformed mixture of components, which comprises a liquid fuel and a metered amount of solvatosol. The solvatosol comprises spherical carbon nano clusters CNOs to the extent from 1 to 500 nm; these clusters consist of laminated partially closed cockleshell-like form graphene layers, and additionally contain as substituents functional groups, notably amino groups and heterocyclic bases containing oxygen, hydrogen, nitrogen to the extent from 1 to 700 atoms. Activation of a mixture is performed by applying of different mechanical stirrers.

Carbon nanosized spherical clusters CNOs are obtained by arc synthesis in cyclohexane. Using as a raw the mixture of hydrocarbons leads to the formation of carbon nano-sized spherical clusters CNOs, having a complex hierarchical structure, which is characterized by "onion-like" structure: individual nanoparticle consists of laminated partially closed cockleshell-like form graphene layers, inside of which is disordered carbon nucleus. Individual particles are collected in agglomerates, have a spheroid shape, size to 500 nm and the interplanar distance d is 3,5727 ± 0,015 A.

A characteristic feature of spherical nano clusters CNOs is that they contain endohedral inclusions of metal atoms (Cr, Mn, Fe, La, Ni, Co), which was confirmed by X-ray fluorescence analysis. In the capacity of liquid fuel the motor fuel contains hydrocarbon fuel and bioethanol fuel and mixtures thereof. In the capacity of an additive for motor fuels serves the solvatosol of nanosized spherical carbon cluster CNOs to the extent from 1 to 500 nm; these clusters consist of laminated partially closed cockleshell-like form graphene layers, and additionally in the capacity of substituents contain the functional groups (amino groups, heterocyclic bases) with halogens (F, CI, Br), oxygen, hydrogen, nitrogen to the extent from 1 to 700 atoms. The nanoparticles were characterized by elemental and physical-chemical analysis, as well as Raman spectra, IR spectroscopy, X-ray fluorescence analysis and atomic force microscopy.

Obtained motor fuel is chemically stable under sunlight, at low temperatures as well as moisture and in touch with condensed commercial water in an amount up to 4% by volume. The following are specific examples of preparation of motor fuel for internal combustion engines.

Example 1.

For obtaining a motor fuel is carried out blending of hydrocarbon fuel taken in an amount of 99.9 wt. % with the additive that is solvatosol of spherical carbon nano clusters CNOs, taken in an amount of 0.1 wt.%. Compounding is carried out at ambient temperature, followed by stirring using a mechanical stirrer.

Example 2.

For obtaining a motor fuel is carried out blending of hydrocarbon fuel taken in an amount of 14.9 wt.%, bioethanol taken in an amount of 85.0 wt.% with the additive that is solvatosol of spherical carbon nano clusters CNOs, taken in an amount of 0.1 wt. %. Compounding is carried out at ambient temperature, followed by stirring using a mechanical stirrer.

Example 3.

For obtaining a motor fuel is carried out blending of hydrocarbon fuel taken in an amount of 8.0 wt.%, bioethanol taken in an amount of 81.9 wt.% with the additive that is solvatosol of spherical carbon nano clusters CNOs, taken in an amount of 0.1 wt. %. Compounding is carried out at ambient temperature, followed by stirring using a mechanical stirrer.

Research of motor fuels' properties have been carried out at the Institute of Bioorganic Chemistry and Petrochemistry of National Academy of Sciences of Ukraine, 10th Chemmotological center of the Ministry of Defense of Ukraine and Research Laboratory of nanotribotehnology at National Aviation University of Ukraine. The results are shown in the table.

Property Samples Prototype

Jfc 1 JV° 2 JY^O 3 JV°4

1 Hydrocarbons content

(% volume) 99,9 14,9 8,0 0,2

2 Bioethanol content (% - 85,0 91 ,9 99,7 volume)

3 Additive content (% 0,1 0,1 0,1 - weight)

4 Colour pale pale pale colourless yellow yellow yellow

5 Density at the

temperature 20°C, kg/m³ 749 782,7 767,0 793,0

6 Water (% volume) 0,01 0,03 0,03 0,05

7 The octane number

- research method 92,1 107,9 99,7 1 1 1

- motor method 83,2 96,5 90,2 103

8 Vapor Pressure at 25 °C, 51 44,2 47,8 37,8

kPa

9 Copper plate test satisfies satisfies satisfies satisfies

10 The value of the

frictional wear of the 0,96 0,55 0,85 1 ,73 node, mem

1 1 Critical scoring load of

frictional unit, N 120 90 100 80 Testing of motor fuels' characteristics were carried out as follows:

- Testing of color performed visually in accordance with State Standard 4063-2001 ;

- Testing of density was carried out at a temperature of 20 ⁰ C in accordance with State Standard 3900;

- Testing of water volume fraction was carried out in accordance with ASTM E 1064;

- Testing of anti-knock performance was carried out in accordance with State Standard 8226;

- Testing of saturated vapor pressure was carried out in accordance with State Standard 1756;

- Copper plate test was performed in accordance with State Standard 6321 ;

- Testing of the value of the frictional wear of the node was carried out on the friction test machine of Measuring and test complex NAU-01 with constant contact loads (with auto settings, 3D).

Quality assessment of test samples on their antiscoring and antiwear properties was carried out in conditions of friction, as close as possible to the real conditions of the mechanism and the specific friction unit. As the test samples of model friction unit were selected the rollers with diameter of 3mm and thickness of 3mm which were specifically made of steel BSAC-15 (bearing steel alloyed by chrome; chrome content is 1,5% weight).

The tests were carried out on the friction test machine with constant contact loads. Axial load - 80N, ambient temperature - 18 ° C; co = 300 min^"1. The estimation of antiscoring and antiwear properties of four fuel samples by measuring the wear of the friction surface (microns) followed the tests.

It was established that the using of motor fuels with additive based on carbon spherical clusters leads to environmental performance of gasoline. Investigation of energy and environmental characteristics of the engine was carried out on the engine test rig with the engine MeMZ307.1, which worked on a fuel sample indicated as "sample _Ne2" in the table, and the automobile gasoline A-95. We found that when working on fuel "sample N_> 2" engine has an output of 103.3% compared to the power generated by motor gasoline A-95.

It is shown that at engine work on fuel "sample N° 2" exhaust emissions significantly reduced compared with the engine work on automobile gasoline A-95: more than 2 times decreased the concentration of CO and CnHm, and on a mode of power rating nitrogen oxides NOx contain reduced by 3 times .

Thus, the motor fuel at the expense of introduction in its composition of fundamentally new additives allowed not only to solve the problem of increased details wear, but also to receive the fuel with improved energy and environmental indicators.

It is possible to use the developed motor fuel containing novel additives in auto transport industry. Motor fuel is intended for use in the latest automotive internal combustion engines with increased compression, increased pressure in the fuel system, with high demands on the content in the exhaust gases of sulfur compounds and other aggressive to the catalyst incinerator components and has appropriate characteristics: increased detonation resistance, improved environmental and tribological characteristics. References

1. ΠατεΗτ 67889 UA, ΜΠ CIOL 1/02, ClOLl/14, ClOLlO/02

"ΚθΜΠ03ΗΙίΪΛ najiHBHa cyMimeBa pjia flBHryHlB BHVTpilllHbOrO 3ΓθρΛΗΗ«", ony6ji. 12.03.2012 6K)JI. Ji 5

2. International Publication WO2007145490 (Al), the IPC CIOL 1/02, C IOL 1/14, CI OL 10/02. "Alternative fuel preventing phase separation and corrosion for internal combustion engines" / Lee Yong Man, Publ. 21.12.2007

3. ITaTeHT Jis 67888 UA, ΜΠ CIOL 1/02, C 10L1/14, C10L10/02. "MoTopHe 6ioeTaHOJibHe najiHBo", onyGji. 12.13.2012 EKWI. Ne 5

Claims

1. Motor fuel containing liquid fuel and additive, which is characterized in that it contains in the capacity of additive the solvatosol of carbon nanosized spherical clusters CNOs to the extent from 1 to 500 nm; these clusters consist of laminated partially closed cockleshell-like form graphene layers, and additionally in the capacity of substituents contain functional groups, notably amino groups and heterocyclic bases including oxygen, hydrogen, nitrogen to the extent from 1 to 700 atoms in the following ratio of components, wt. %:

Liquid fuel - 90,5 - 99,999;

Additive - 0,001 - 9,5.

2. Motor fuel according to claim 1 , which is characterized in that in the capacity of liquid fuel is used a mixture of hydrocarbon fuel and motor bioethanol fuel in the following ratio of components, wt. %:

- Hydrocarbon fuel - 0,001 - 99,999;

- Motor bioethanol fuel - 0,001 - 99,999.

3. Motor fuel according to claim 1, which is characterized in that the carbon nanosized spherical clusters consisting of laminated partially closed cockleshell-like form graphene layers contain endohedral atoms including rare earth, transition and heavy metals(Chromium, Manganese, Iron, Lanthanum, Nickel, Cobalt).