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ПОЛ1ПШЕННЯ ЯКОСТ1 ВУГЛЕВОДНЕВИХ ПАЛИВ З ВИКОРИСТАННЯМ МУЛЬТИФУНКЦЮНАЛЬНИХ ПРИСАДОК
Рок 1.В.
Нацюнальний технгчний утверситет Украти «Кшвський полтехтчний iнститут 1мет 1горя Сжорського», асистент
Кшв
QUALITY IMPROVEMENT OF HYDROCARBON FUELS WITH USING MULTYFUNCTIONAL ADDITIVES
Roik I.V.
National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute", Teaching Assistant
Kyiv
АНОТАЦ1Я
Проаналiзовано сучасний ринок присадок до палива та розроблено компонентний склад паливних добавок на основi поверхнево-активних речовин та антиоксиданпв. Було розроблено ряд добавок, яш скла-даються з антиоксиданпв рiзноi хiмiчноi природи та поверхнево-активних речовин. Паливна добавка за сво!м компонентним складом е рослинного походження i бюлопчно розкладаеться. Вперше було отримано композицшну багатофункцюнальну присадку до бензину, яка складаеться з антиоксиданпв з рiзною тер-мiчною стаб№нютю, i шдтверджено синерпзм ]_'х ди. Виявлено, що використання добавок у визначеному дiапазонi значень покращуе експлуатацiйнi та екологiчнi властивосп палива. Концентрацiя оксиду Карбону (II) СО знижуеться на 4-10 %, вмют вуглеводнiв CxHy - на 3-6 %. Отримано зменшення споживання палива на 3-5 %.
ABSTRACT
It was developed some series of additives, which consist of antioxidants of different chemical nature and surfactants. This technology is a fuel additive of vegetal origin and biodegradable, thus resulting in a renewable and inexhaustible source of energy due to its vegetal origin. For the first time, it was obtained the multifunctional fuel additive that consists of antioxidants with different thermal stability and it was determine the synergetic effect of their action. It was found that using of the additives in determined volume diapason significantly improves operational and environmental properties of fuels. The concentration of carbon monoxide (II) CO reduced by 410%, total hydrocarbons CxHy- by 3-6%. There was also a reduction of fuel consumption by 3-5%.
Ключовi слова: автомобшьний бензин, присадки, антиоксиданти, поверхнево-активш речовини, ви-трата палива.
Keywords: automobile gasoline, additives, antioxidants, surfactants, fuel consumption.
PROBLEM STATEMENT. The reduction of global oil reserves and high prices on traditional motor fuels and the ever-increasing requirements to exhaust emissions of engines require measures to reduce the consumption of petroleum products and improve their quality. Most fuels such as gasoline, kerosene (jet fuel), gas oil (diesel fuel) and fuel oil have drawbacks which do not allow their long term storage, make difficult transportation and even usage. About 20 properties of fuels can be improved, maintained or imparted new beneficial characteristics by adding of small amounts of certain chemicals named fuel additives.
ANALYSIS OF RECENT RESEARCH AND PUBLICATIONS. Rapid growth of the cars fleet and its inconsistency to current European standards cause increasing of energy consumption and, consequently, cause air pollution by emissions of carbon monoxide, nitrogen oxide, hydrocarbons, etc. Therefore, the problem of reducing the negative impact of transport on the environment is of high importance. Among the existing methods of reducing the concentration of harmful exhaust gases emissions of internal combustion engines that run on gasoline, one of the most promising is the use of additives to fuel (Nikitina et al., 2010) [1, p.6].
Fuel additives are added in very small concentrations: from several ppm to several thousands ppm. It is important that additives which improve some properties should not deteriorate other properties of fuels and its quality in general. The main types of additives, which are used in hydrocarbon fuels, are showed at the table 1.
Fuel additives are organic substances soluble in fuels: antifoams, anti-icing additives, anti-knock additives, antioxidants, antistatic additives, anti-valve seat recession additives, biocides, cetane improvers, combustion chamber deposit modifiers, corrosion inhibitors, demulsifiers, deposit control additives, detergents, diesel fuel stabilizers, drag reducing agents, dyes and markers, leak detector additives, lubricity improvers, metal deactivators, and wax anti-settling additives.
Fuel additives are chemical substances that are added to gasoline, diesel and other fuels to impart or improve some properties (Danilov, 2000). It is known several types of widely used additives such as:
- octane-enhancing additives (improve octane ratings);
- anti-oxidants (inhibit gum formation, improve stability);
- metal deactivators (inhibit gum formation, improve stability);
- deposit modifiers (reduce deposits, spark-plug fouling and preignition);
- surfactants (prevent icing, improve vaporization, inhibit deposits);
- reduce NOx emissions;
- freezing point depressants ( prevent icing );
- corrosion inhibitors (prevent gasoline corroding storage tanks);
- dyes (product colour for safety or regulatory purposes ).
The main types of additives, which are used in hydrocarbon fuels, are showed at the table 2.
Leading players of this industry have been profiled with their recent developments and other strategic industry activities. These include, The Lubrizol Corporation (U.S.), Innospec Inc. (U.S.), Afton Chemical Corporation (U.S.), Infineum International Ltd (U.K.), Fuel Performance Inc. (FPS) (U.S.), BASF Corporation (Germany), Cerion Energy (U.S.), Chevron Oronite Company LLC (U.S.), Cummins Filtration Inc. (U.S.), Chemtura Corporation (U.S.), Total Petrochemicals and Refining (France), Evonik Industries AG (Germany), Dorf-Ketal Inc.(India), and Albemarle Corp (U.S.).
Innovation is an on-going requirement in the fuel additives business, often driven by legislation which changes the specification of fuels (not only automotive fuels) or demands the use of higher quality fuels. Reduction of sulfur content in middle distillate fuels, for example, has led to the need to develop lubricity additives to protect diesel injector pumps. In another instance, there may be the need to develop a new and enhanced multi-functional additive package (possibly including novel additive components) to enable vehicle fuel economy to be improved while minimizing the emission of regulated exhaust pollutants. Growth in the demand for diesel exhaust particulate filters, for example, has spurred the development of fuel borne catalyst additive products to assist on-board filter cleaning, or regeneration, of the particulate filter.
To avoid peroxide production after the refinery process a specific antioxidant additive should be added on fuel. The antioxidants generally used are based on hindered phenols in a range of concentration 10-20 mg/ ml (M. Bernabei et al., 2000) [2, p. 235-241].
Antioxidants (inhibitors of fuel oxidation). Gasoline, jet fuel and diesel fuel contain unstable unsatu-rated hydrocarbons (olefins and diens) which can polymerize and form gums. The gums are carried forward into the engine system, and can lead to its malfunctioning and breakdown. In addition, olefins and diens containing in gasoline react more readily with dissolved oxygen than the other classes of hydrocarbons. The chain of oxidation reactions can result in formation of hydroperoxides (ROOH) and peroxides (ROOR) in fuels [4, p. 56-60].. They are highly oxidizing agents resulting in increase of corrosiveness of fuel. Such problems (to stabilize the fuel and reduce the tendency for gum to form) can be avoided by injection of antiox-idant chemicals. An antioxidant is a molecule that inhibits the oxidation of other molecules.
Oxidation can produce free radicals which can start chain of oxidation reactions in fuels. Antioxidants work by interrupting this chain of reactions (removing free radical intermediates), preventing the formation of hydroperoxides, peroxides, soluble gums, or insoluble particulates.
Table 1
Types of additives to hydrocarbon fuels
Type Treat Level
Wax anti-settling additives 100-200 mg/kg
Antifoam additives 2 - 10 mg/kg
Anti-valve seat recession additives 100 - 200 mg/kg
Pipe line drag reducing agents 2 - 20 mg/kg
Diesel detergency additives 10 - 200 mg/kg
Demulsifiers 3 - 12 mg/kg
Diesel flow improvers 50 - 1000 mg/kg
Deposit control additives 100 - 1000 mg/kg
Lubricity improvers 25 - 400 mg/kg
Anti-static additives 1 - 40 mg/kg
Diesel stabilisers 50 - 200 mg/kg
Anti-icing additives 0.1 - 2 vol %
Corrosion inhibitors 5 - 100 mg/kg
Combustion chamber deposit modifiers 50 - 400 mg/kg
Metal deactivators 4 - 12 mg/kg
Anti-oxidants 8 - 100 mg/kg
Dyes 2 - 20 mg/kg
Lead anti-knock additives 0.15 g Pb/l max
Cetane improvers 100 - 1000 mg/kg
Antioxidants do this by being oxidized themselves instead fuels. Antioxidants are often reducing agents, such as hindered phenols, aromatic amines and diamines, or mixtures of aromatic diamines (e.g., phenylenediamines) and alkyl phenols. Antioxidants became more important in the 1970s when increased the concentrations of olefin compounds in fuels. Antioxidants are the biggest gasoline additives. They are also used in aviation gasoline, jet fuel, diesel fuel, and biofuel Prior to now antioxidants were injected as close as possible to producing of fuels at oil refineries [5, p. 201-210]. However, nowadays it is clear that nothing to hurry to inject them.
So, the analysis of the literature has showed the expediency of developing multifunctional additives for hydrocarbon fuels which would improve their physical and chemical properties, prevent the formation of deposits, and promote energy conservation and air quality improvement.
The purpose of the research is to investigate the influence of multifunctional additives based on antioxidants on hydrocarbon fuels characteristics.
EXPERIMENTAL PART AND RESULTS OBTAINED. Antioxidants significantly slow down the fuel degradation process. According to their mode of action, antioxidants could be classified into various groups: free radical terminators, metal ion chelators capable of catalyzing lipid oxidation, or as oxygen scavengers that react with oxygen in closed systems. Free radical terminators are considered primary antioxidants, which react with high energy lipid radical sand convert them into thermodynam-ically more stable products. Phenolic antioxidants (AH) are recognized as free radical terminators and these are mostly used antioxidants. Secondary antioxidants work by impending the rate of chain initiation by decomposing the hydroperoxides (I.M. Rizwanul Fattah et al., 2014.) [3, p. 356-370].
Table 2
Composition of Multifunctional additives
№ Antioxidants Surfactants
1 2,6-ditretbutyl -4 -methylphenol Non-ionogenic: 1) Ethoxylated fatty alcohol (R = C14-C16) 2) DEA of rapeseed oil (R = C12-C18) Ionogenic: Ammonium oleate
2 N-Methyl-N,N-bis-(3,5-di-4-tretbutyl hydroxybenzyl)amine
3 2,2'-Methylene-bis-(4-methyl-6-tretbutylphenol)
4 4- isononyl -2-(aminomethyl -3',5'-dytretbutyl- 4'-hydroxyphenyl)phenol
5 4,4 -Dioktyldiphenylamine
It was developed some series of additives, which consist of antioxidants of different chemical nature and surfactants (tabl. 2) [6]. It is important that these surfactants are made of renewable sources. This technology is a fuel additive of vegetal origin and biodegradable, thus resulting in a renewable and inexhaustible source of energy
due to its vegetal origin. Usage of these additives to gasoline is an effective method of preventing formation of deposits in the fuel system, and preserving factory engine setting, and eliminates the pollutants emissions.
It has been selected a number of antioxidants, which differed in thermal stability (Tabl. 3).
Table 3
Thermal stability of antioxidants of different chemical classes
№ Name of antioxidant Temperature of losing mass, °C
10 % 50 %
1 2. 6 -ditretbutyl -4 -methylphenol 110 140
2 N-Methyl-N,N-bis-(3,5-di-4- tretbutylhydroxybenzyl) amine 195 230
3 2,2'-Methylene-bis-(4-methyl-6-tretbutylphenol) 215 254
4 4- Isononyl -2-(aminomethyl -3',5'-ditretbutyl- 4'-hydroxyphenyl)phenol 203 287
5 4,4' -Dioktyldiphenylamine 205 290
Besides, the effect of additives on the combustion processes has been studied. Reaction of cold flame oxida-
- - —I— —1—
rn
oc-• .
-
I s i 1 1 tl u I » 1 <
1 Time.s
tion for samples of gasoline A-95, with developed additives (0,5 % vol.) is presented on graphs (Fig. 1) [7, p. 1216].
X
0- ... —
; i i 1 10 1 1} 1 4 1 «
2 Time.s
IOC"
TO
3o-
« r i » to It 11 tl U U H Time ,s
Figure 1 - Reaction of cold flame oxidation for samples of gasoline A-95, with developed additives (0,5 % vol.) (1 - 2.6-Ditretbutyl-4-methylphenol; 2 - N-Methyl-N, N-bis-(3,5-di-4-tretbutylhydroxybenzyl)amine; 3 - 4,4'-
Dioktyldiphenylamine)
It was observed that the induction period of fuel depend on the thermal stability of antioxidants. The higher is the stability of antioxidants - the higher induction period. This, in turn, contributes to the completeness of combustion and lower exhaust emissions. The effect of additives on the combustion processes has been studied.
CONCLUSIONS. The results of the research confirmed that the additive for fuels that contains 4,4'-Dyok-tyldyfenilamin as an antioxidant in the amount of 0,1 % vol. increases the induction period from 1,45 seconds to 2,25 seconds. According to these results the components of the hydrocarbon fuel additive were chosen (Roik et al., 2014). Laboratory studies of gasoline grade A-95 without and with different concentrations (0.01%, 0.05%, 0.1%, 0.15% vol.) of additives showed that the basic physical and chemical performance of gasoline meets standard Ukrainian requirements. In addition, it was found that using of the additives in determined volume diapason significantly improves operational and environmental properties of fuels. The concentration of carbon monoxide (II) CO reduced by 4-10%, total hydrocarbons - by 3-6%. There was also a reduction of fuel consumption by 3-5%. This allows us to modify the fuel with the improvement of its operational and environmental properties. So, the analysis and research has showed the expediency of developing multifunctional additives for hydrocarbon fuels which would improve their physical and chemical properties, prevent the formation of deposits, promote energy conservation and air quality improvement.
References
1.Nikitina, E., Pavlov, D. (2010) "Detergents for Gasoline - Step-by-Step. The History of Developmen ", Scientific and Technical Journal "World of Oil Products. The Oil Companies' bulletin", no. 1, pp. 3-9.
2.Bernabei, M., Bocchinfuso, G. Carrozzo, P., Ange-lis, C. (2000) "Determination of phenolic antioxidants in aviation jet fuel", Journal of Chromatography A 871, pp. 235-241.
3.I.M. Rizwanul Fattah et al. (2014) "Effect ofanti-oxidants on oxidation stability of biodiesel derived from vegetable and animal based feedstocks', Renewable and Sustainable Energy Reviews, no.30, pp. 356-370.
4.Obadiah A, Kannan, R, Ramasubbu A, Kumar (2012) "Studies on the effect of antioxidants on the long-term storage and oxidation stability", Fuel Process Tech-nol, no. 99, pp. 56-63.
5.Bolland J, Ten Have P. Kinetic studies in the chemistry of rubber and related materials. The inhibitory effect of hydroquinone on the thermal oxidation of ethyllinole-ate. Trans Faraday Soc, no.43, pp.201-210.
6.Roik, I., Vasylkevych, O., Stepsnov, M., (2014) Gasoline Additive which contains high temperature anti-oxidants. Patent UA 93246.
7.Roik, I., Vasylkevych, O., Stepsnov, M., Bondarenko S. "Evaluation of influence of multyfunc-tional additives on operational and technical parameters of petrol', Eastern-European Journal of Enterprise Technologies, no. 6(63), pp.12-16.
