Все более усугубляющаяся экологическая напряженность, вызванная негативными последствиями использования минеральных энергоисточников, делает актуальной проблему получения  экологически более безопасных  бензиновых и дизельных топлив.  Если учесть, что автомобильные двигатели обеспечивают до  80%  выбросов токсичных веществ в атмосферу,  то одним из приоритетных направлений получения моторных топлив является улучшение их экологических показателей, в первую очередь – показателей токсичности отработавших газов [1,2].

Как  эффективное средство улучшения названных показателей рассматривается применение различных кислородсодержащих добавок к топливам, в качестве которых используются спирты и эфиры[3,4]. Наличие атомов кислорода в этих добавках обеспечивает более полное сгорание топлив, что делает продукты их сгорания экологически безопасными [5,6].

В представленной работе изучены физико-химические и эксплуатационные характеристики дизельного топлива при добавлении в его состав 1,0-5,0% масс. оксипропиловых эфиров природных карбоновых кислот, синтез которых проведен в автоклаве при соотношении кислота:оксипропилен 1:1-1:4 при температуре 100-150 ^оС с использованием щелочного катализатора. В качестве природных карбоновых кислот использованы побочные продукты щелочной очистки дизельных фракций. Качественные характер

It was studied the physicochemical properties of diesel fuel with a content of 1-5% dehydrated (99.5%) and watered (93%) n-butanol. To obtain homogeneous mixtures, a rotary-type mixer was used at temperatures of 0-25 ° C. It was found that the stability of diesel fuel containing 3% mass. dehydrated n-butanol at room temperature is 60 days. An increase in the content of n-butanol to 5% leads to a decrease in the stability of the prepared mixture up to 45 days. The stability of the diesel fuel mixture with 3% 93% n-butanol is 5 days at normal, and not more than 3 days at a temperature of 0 ° C. Adding to this mixture a 1% emulsifier obtained on the basis of propylene oxide esters with petroleum acids makes it possible to obtain homogeneous diesel fuel while preserving all its physicochemical properties. In addition, it was found that when this mixture is burned, the content of toxic gases, such as carbon oxides, nitrogen and sulfur, in the exhaust gas composition decreases by 24%, 16% and 12%, respectively, in comparison with the burning of butanol-free diesel fuel.

1. INTRODUCTION. Last trends in environmental restrictions make it necessary to upgrade the usage of alternative types of raw materials used for transportation purposes such as motor fuels, bio-based alcohols and other oxygen containing components. Based on that by using environmentally friendly raw materials for producing automotive fuels such as diesel is the main objective of today’s industry. Compared to other lighter fossil derived fuels diesel engine produce more particulate matter-PM, more smoke, and nitrogen oxides-NOx with high thermal efficiency and lower carbon monoxide-CO and hydrocarbon-HC emissions. Specifically, the reduction of NOx and smoke emissions by Exhaust Gas Recirculation (EGR), the variety of catalytic converters, high-pressure injection systems and as well as oxygenated fuels were investigated by many researchers. The major challenge associated with diesel engine is the use of different alcohols in higher percentage mixed with diesel fuel. But the limited capability of miscibility at a lower temperature and the required minimum modification in fuel delivery systems restrict the use of alcohols in diesel fuel. By looking to the statistics, the automobile engines provide more than 80% of emissions to the atmosphere while the share of road transport in the emission of harmful substances reached up to 5 kton per day [1]. Ethers of fatty acids and alcohols are one of alternative ways of using oxygen containing components where the indicative parameters of the engine fuels can be improved. Indeed, the presence of oxygen atoms in these….

1. INTRODUCTION. Crude oil is depleting fossil resource, and to maintain the production and supply has been a recurrent concern for last period. Tightened environmental restrictions makes it necessary to facilitate the usage of alternative types of raw materials to be used for transportation purposes such as motor fuels, bioethanol and other alcohols. From other perspective usage of fossil derived fuels is decreasing day by day because of crude oil unavailability, unstable world crude and petroleum products prices, and the stringent environmental regulation. Therefore, it requires environmentally friendly raw materials application for producing automotive fuels such as diesel.

Automobile engines provide more than 80% of emissions to the atmosphere whereas if looking to the figures, the share of road transport in the emission of harmful substances is around 60.6%, 33.5% and 32% in USA, UK and France accordingly while the emission level annually by motor vehicles reaches up to 1.7 million tons [1,2]. That is reason of trying towards the improving the composition of motor fuel up to environmental wellness level in terms of relieving exhaust toxicity rates.

Applying different oxygen containing additives such as alcohol and ethers of fatty acids is one of the most effective ways, where the quality parameters of the engine fuels can be improved reasonably. In fact, the presence of oxygen atoms in these types of additives provides a more complete combustion of the fuel, which makes the products combustion environmentally safe. Since these fuels is almost non-depleted raw material base – both mineral (natural gas, coal, oil shale) and organic (potato, beet, vegetable oils and their waste, algae, etc.) it given a special advantage of using these components [2-6]. Because of availability of ethanol production, the use of alcohols as additives in diesel fuels, such as ethanol, is more economically feasible. Based on that, in general there are two main possible ways to use ethanol, either in the form of an emulsion of mineral diesel fuel and watered alcohol (i.e., azeotropic mixture of ethanol and water), or in the form of a mixture of diesel fuel and absolute (anhydrous) alcohol. Applying one of these two….

1.GİRİŞ.

Dünya miqyasında atmosferə atılan zərərli qazların mənbələri sırasında avtomobil mühərrikləri mühüm yer tutur. Statistik göstəricilərə nəzər salsaq, zərərli maddələrin tullantısında yol nəqliyyatının payı dünyanın aparıcı ölkələrində üstünlük təşkil edir. Ümumilikdə avtonəqliyyat vasitələri ilə hər il atmosferə 1,7 milyon tondan çox tullantı qazı buraxır [1-3]. Bu baxımdan aparıcı neft və qaz şirkətləri, eləcə də elmi-tədqiqat mərkəzləri mümkün atmosfer çirklənməsini azaltmaq məqsədi ilə mühərrik yanacaqlarının tərkibini ekoloji sağlamlıq səviyyəsinə qədər optimallaşdırmaq üçün intensiv tədqiqatlar həyata keçirtməkdədirlər.

2. MƏSƏLƏNİN QOYULUŞU

Spirt və yağ turşularının efirləri kimi müxtəlif oksigenli əlavələrdən istifadə edərək mühərrik yanacağının keyfiyyət parametrlərini əsaslı şəkildə yaxşılaşdırmaq mümkündür. Bu növ aşqarlarda oksigen atomlarının olması yanacağın yanma kamerasında daha tam yanmasını təmin edir ki, bu da yanma məhsulların göstəricilərinin ekoloji normalar səviyyəsində saxlayaraq təhlükəsiz edir [4-5].

Dünya miqyasında etanol istehsalatlarının artıq mövcud olmasını nəzərə alaraq, dizel yanacağına əlavələr kimi istifadəsi iqtisadi cəhətdən çox səmərəlidir. Buna əsaslanaraq, dizel yanacağı ilə birgə etanolun istifadəsinin sulu spirt (yəni etanol və suyun azeotropik qarışığı) və susuz spirt şəklində mümkün tədbiq yolları vardır. İstənilən qarışıq üsulunu tətbiq etməklə dizel mühərriklərində yandırılan yanacaq əsasında ətraf mühitə atılan tullantıların miqdarı baxımından  əhəmiyyətli dərəcədə azalır və bu əsasən aşağıdakı amillərlə bağlıdır [6-7]:

– etanolun buxarlanma istiliyinin yüksək olması səbəbindən (etanol üçün 870 kJ/kq, dizel yanacağı üçün 230-250 kJ/kq) yanma kamerasında temperaturun aşağı düşməsi və nəticədə atmosferə atılan azot oksidlərinin azalması

– yanacağın yanması zamanı yanacağın tərkibindəki etanol molekullarında olan oksigen atomlarının olması –  etanolun aşağı qaynama həddi (78,4°C-dir lakin dizel yanacağı üçün isə 160-360°C təşkil edir) dizel yanacağının yanması zamanı işlənmiş qazların toksiklik dərəcəsini azaldır. Belə ki, qarışıqdan etanolun sürətli buxarlanması səbəbindən dizel yanacağın yanması zamanı əlavə turbulens təsir yaranır. Eyni təsir dizel yanacağına əlavə edilmiş emulqatorların mühərrikdə

Absract

The limited oil resources and the tightening of the environmental measures of both the fuels  and their combustion products makes it necessary to use alternative types of raw materials for the production of motor fuels, such as bioethanol and other alcohols. This article presents the results of obtaining the diesel fuel with a content of up to 5% watered and dehydrated ethanol. Experiments on the production of diesel-ethanol compositions were carried out at the temperature range of 0–25 ° C with mixing of mixtures using a rotary mixer and an ultrasonic sonotrode with an oscillation frequency of 20 kHz. It was revealed that the stability of diesel-alcohol compositions on using dehydrated ethanol in the composition of diesel fuel to 3% mass. at room temperature is 30 days. The increase of the ethanol content in the diesel fuel composition reduces the stability period of obtained mixture to 25 and 18 days, respectively. For low temperatures, the reduction at the period of stability of the compounds is up to 10 days for 1-2%, 8-5 days for 3-5% compounds, respectively.

On using watered ethanol, even when it is contained in diesel fuel 1% during mixing with an agitator with a turnover rate of 600 rpm, an unstable emulsion forms, which stratifies after a few minutes. The increase of ethanol content in composition of diesel fuel leads to the formation of an even less stable emulsion. However, on mixing the obtained compounds using an ultrasonic sonotrode, slightly coalescing mixtures are formed, the stability of which is no more than 10 days at room temperature and 5 days at low temperature.

Using the method of dynamic light scattering, the dynamics of changes in the size of droplets of watered ethanol in diesel fuel composition with time was investigated and it was established that on the day of preparation of compositions the size of ethanol drops in diesel fuel composition for 3% compound at room temperature is 150-160 nm. On the 5th day after preparation of the compound, the particle size of ethanol increases to 800-900 nm, after which there is a rapid separation of the mixture into diesel and ethanol layers.

To preserve the emulsion of diesel fuel using watered ethanol, an emulsifier obtained on basis of petroleum acids and propylene oxide have been used. Revealed that the addition of it to the composition of the 3% composition of ethanol with diesel fuel ensures the production of homogeneous diesel fuel with retention of all its normalized parameters. The particle size of ethanol in the diesel fuel composition on the day of preparation is 2-7 nm, on the expiry of 20 days the ethanol droplet size increases to 80-90 nm, which ensures the long-term stability of the obtained compound.

It was revealed that, despite the water content of ethanol, the use of this emulsifier ensures the production of homogeneous diesel fuel while retaining all its normalized measures. Reducing the content of carbon monoxide, sulfur oxides and nitrogen in the composition of exhaust gases is 28%, 24% and 16%, respectively.

Keywords :      Alternative feedstock, ethanol, emulsifier, exhaust gas composition

Intriduction

Feedstock deficit, unstable world crude and petroleum products prices, and the stringent environmental regulation causes negative effects for the use of mineral energy sources makes it actual of involvement of alternative energy sources and at the same time more environmentally friendly raw materials in the processes of producing commodity fuels such as gasoline and diesel.

Considering the automobile engines provide up to 80% of emissions of toxic substances into the atmosphere (for example, the share of road transport in the emission of harmful substances is 60.6% in the USA, 33.5% in UK, 32% in France, in Moscow and Beijing – 80%, while the annual total emissions of harmful substances by motor vehicles in these cities reach up to 1.7 million tons / year), then one of the priorities for the production of motor fuels is to improve their environmental wellness such as exhaust toxicity rates [1,2]. In the most effective ways, the quality parameters of the mentioned products can be improved by using different oxygen containing additives such as alcohol and ethers (for gasoline and diesel fuel) and alkyl esters of fatty acids (for diesel fuels). The presence of oxygen atoms in these additives provides a more complete combustion of the fuel, which makes the products combustion environmentally safe. The feasibility

Аннотация

       В качестве кислородсодержащей добавки к товарным дизельным топлива (ТДТ) исследованы сложные эфиры природных карбоновых кислот и окиси пропилена (СЭККОП) в чистом виде и при добавлении в состав товарного дизельного топлива до 5% этанола (95 и 99,9%-ного).  Выявлено, что для 5%-ных компаундов СЭККОП с ТДТ увеличение температуры вспышки составляет 3^оС, снижение температуры застывания 20^оС (до -45^оС), также наблюдаются уменьшение коксуемости и содержания ароматичечских углеводородов.. Улучшение состава выхлопных газов при использовании 3-5%-ных компаундов СЭККОП с ТДТ заключается в снижении содержания монооксида углерода на 20-30%, с одновременным снижением содержания оксидов серы и азота на 0,3-1,5% масс.

Исследованы качественные показатели товарного дизельного топлива с содержанием в нем до 5% этанола  (95%- и 99,9%ного) в чистом виде и с использованием   СЭККОП в качестве поверхностно-активного эмульгатора.  Выявлено, что, несмотря обводненность этанола,  использование данного эмульгатора обеспечивает  получение однородного дизельного топлива с сохранением всех его нормируемых показателей. Уменьшение содержания монооксида углерода, оксидов серы и азота в составе выхлопных газов составляет  28%, 24% и 16% соответственно.

Ключевые слова:    товарное дизельное топливо , этанол, эмульгатор, состав выхлопных газов, сложные эфиры карбоновых кислот, окись пропилена

Дефицит нефтяного сырья, нестабильность мировых цен на нефть и нефтепродукты, а также все более усугубляющаяся экологическая напряженность, вызванная негативными последствиями использования минеральных энергоисточников, делает актуальной проблему вовлечения альтернативных и одновременно экологически более безопасных  видов сырья в процессы получения бензиновых и дизельных топлив.  Если учесть, что автомобильные двигатели обеспечивают до  80%  выбросов токсичных веществ в атмосферу (например, доля автомобильного транспорта в выбросе вредных веществ составляет в США – 60,6 %, в Англии – 33,5 %, во Франции – 32%,  в Москве, Пекине – 80%, при этом годовые суммарные выбросы вредных веществ автотранспортом  в этих городах достигают 1,7 млн. т/г ), то одним из приоритетных направлений получения моторных топлив является улучшение их экологических показателей, в первую очередь – показателей токсичности отработавших газов [1,2] .

В качестве эффективного средства улучшения названных показателей рассматривается применение различных кислородсодержащих добавок к топливам, в качестве которых используются спирты и эфиры (для бензиновых и дизельных топлив ) и алкиловые эфиры жирных кислот (для дизельных топлив). Наличие атомов кислорода в этих добавках обеспечивает более полное сгорание топлив, что делает продукты их сгорания экологически безопасными. Целесообразность использования этих топлив также заключается  практически в  неисчерпаемой сырьевой базе  –  как минеральной  (природный газ, уголь, горючие сланцы), так и органической (картофель, свекла, растительные масла и их отходы, водоросли и др.) [2-6].

Алкиловые эфиры жирных кислот растительных масел, получаемые на основе растительных масел и простых спиртов,  уже давно и успешно  используются  в качестве  ресурсоповышающих добавок и одновременно модификаторов горения дизельных топлив, однако, для их получения требуется специальное производство.

Использование же в качестве добавок в дизельные топлива  спиртов, таких как этанол более экономически  целесообразно, так производство этанола  налажено и не  требует отдельных мощностей получения добавок на его основе.  При этом возможно два пути применения этанола- либо в виде эмульсии  минерального дизельного топлива и обводненного спирта (т.е. азеотропной смеси этанола и воды), либо в виде смеси дизельного топлива  и абсолютного (безводного) спирта. Реализация этих двух направлений использования этанола существенно улучшает экологические показатели дизеля. Это обусловлено следующими факторами. Во-первых, как отмечено выше, наличие в молекулах этанола атома  кислорода способствует снижению вредных выбросов с отработавшими газами двигателей внутреннего сгорания. Во-вторых, высокая теплота испарения этанола (870 кДж/кг у этанола против 230-250 кДж/кг у нефтяного ДТ) приводит к снижению максимальных температур сгорания, и, как следствие, к снижению выбросов оксидов азота.

Еще одним фактором улучшения показателей токсичности отработавших газов  при сгорании дизельных топлив  является повышение качества процесса смесеобразования за счет низкой температуры кипения этанола (78,4 ^оС у этанола против 160-360 ^оС у нефтяного ДТ), что приводит к быстрому испарению этанола из смесевого топлива и дополнительной турбулизации нефтяного дизельного топлива  за счет такого испарения. Этот эффект, отмеченный для широкого спектра эмульгированных топлив [7,8], способствует также и улучшению показателей топливной экономичности дизеля.

Использование абсолютного этанола хотя и менее проблематично при приготовлении смесевых топлив, однако не гарантирует устойчивость данных смесей при низких и температурах [9,10]. В связи с этим тройные системы дизельное топливо-этанол-эмульгатор более целесообразны и требуют  использования дешевых и доступных эмульгаторов, обеспечивающих стабильность спирто-дизельных смесей и не сказывающихся отрицательно на других….

ABSTRACT

In recent days the energy consumption rate increases all over the world and therefore access to clean, environmentally friendly and sustainable energy becoming one of the important factors for economic development. And shortage of fossil fuels and theirs associated environmental impact during engine combustion remains the main reason for investigating alternative energy sources. With this regard several feedstocks have been analysed and used to produce biofuels for different applications. In this article, the different sourced generated feedstocks from biofuels, specifically emulsified biodiesel and related greenhouse gas emissions, impact of bio based fuels combustion to environment compared to fossil fuels are highlighted. Certain recommendation is also suggested to sustain biofuel and emulsified biodiesel production.

World fossil fuel demand is broadening day by day because of increasing the population of world and in order to meet this demand the new petrochemical-refinery facilities that is related to reconstruction and modernization projects are carried out recently by petrochemical companies. And because of huge usage of fossil based fuels the exhaust gasses increases tremendously. In parallel with this exhaust gases derived from the burning of these fuels such as carbon monoxide (CO), sulphur dioxide (SO₂) and nitrogen oxides (NO_x) are basically responsible for the creating the greenhouse effect in the atmosphere, which consequently causes planet global warming. Therefore in these days the significant consideration given to the prosperity and utilization of alternative fuel sources by researchers in order to meet the energy demand as well as improve environmentally friendly fuel production. For instance, one of the main directions for improving the environmental performance of both mineral diesel fuels and their combustion products is also the addition of oxygen-containing additives such as simple alcohols (ethanol, butanol, isopropanol) or methyl (ethyl) fatty acid esters of vegetable oils (biodiesel). The first series of mentioned additives are more preferable, since their production on an industrial scale is already established and does not require the construction of additional production capacities, as required for obtaining biodiesel. However, alcohol- mineral based diesel (biodiesel) mixtures are sensitive to water content, they are less stable; they can decompose easily when the temperature is lowered and require the use of emulsifiers to avoid the above problems. In addition, although bio-based diesels are sensitive to water the use of water is also possible with the selection of appropriate emulsifiers as an oxygen-containing additive to mineral diesel fuels. In general biofuels (or biofuel based fossil fuels) derived from bio-resources basically from biomasses that is the one of main option to replace gradually the fossil fuels due to the fact….

In recent days the energy consumption rate increases all over the world and therefore access to clean, environmentally friendly and sustainable energy becoming one of the important factors for economic development. And shortage of fossil fuels and theirs associated environmental impact during engine combustion remains the main reason for investigating alternative energy sources. With this regard several feedstocks have been analysed and used to produce biofuels for different applications. Different sourced generated feedstocks from biofuels, specifically emulsified biodiesel and related greenhouse gas emissions, impact of bio based fuels combustion to environment compared to fossil fuels to be investigated.

Currently world fossil fuel demand is broadening day by day because of increasing the population of world and in order to meet this demand the new petrochemical-refinery facilities that is related to reconstruction and modernization projects are carried out recently by petrochemical companies. And because of huge usage of fossil based fuels the exhaust gasses increases tremendously. In parallel with this exhaust gases derived from the burning of these fuels such as carbon monoxide (CO), sulphur dioxide (SO₂) and nitrogen oxides (NO_x) are basically responsible for the creating the greenhouse effect in the atmosphere, which consequently causes planet global warming. Therefore in these days the significant consideration given to the prosperity and utilization of alternative fuel sources by researchers in order to meet the energy demand as well as improve environmentally friendly fuel production. For instance, one of the main directions for improving the environmental performance of both mineral diesel fuels and their combustion products is also the addition of oxygen-containing additives such as simple alcohols (ethanol, butanol, isopropanol) or methyl (ethyl) fatty acid esters of vegetable oils (biodiesel). The first series of mentioned additives are more preferable, since their production on an industrial scale is already established and does not require the construction of additional production capacities, as required for obtaining biodiesel. However, alcohol- mineral based diesel (biodiesel) mixtures are sensitive to water content, they are less stable; they can decompose easily when the temperature is lowered and require the use of emulsifiers to avoid the above problems. In addition, although bio-based diesels are sensitive to water the use of water is also possible with the selection of appropriate emulsifiers as an oxygen-containing additive to mineral diesel fuels.

World fossil fuel demand is broadening day by day because of increasing the population of world and in order to meet this demand the new petrochemical-refinery facilities that is related to reconstruction and modernization projects are carried out recently by petrochemical companies. And because of huge usage of fossil based fuels the exhaust gasses increases tremendously. In parallel with this exhaust gases derived from the burning of these fuels such as carbon monoxide (CO), sulphur dioxide (SO₂) and nitrogen oxides (NO_x) are basically responsible for the creating the greenhouse effect in the atmosphere, which consequently causes planet global warming. Therefore in these days the significant consideration given to the prosperity and utilization of alternative fuel sources by researchers in order to meet the energy demand as well as improve environmentally friendly fuel production. For instance, one of the main directions for improving the environmental performance of both mineral diesel fuels and their combustion products is also the addition of oxygen-containing additives such as simple alcohols (ethanol, butanol, isopropanol) or methyl (ethyl) fatty acid esters of vegetable oils (biodiesel). The first series of mentioned additives are more preferable, since their production on an industrial scale is already established and does not require the construction of additional production capacities, as required for obtaining biodiesel. However, alcohol- mineral based diesel (biodiesel) mixtures are sensitive to water content, they are less stable; they can decompose easily when the temperature is lowered and require the use of emulsifiers to avoid the above problems. In addition, although bio-based diesels are sensitive to water the use of water is also possible with the selection of appropriate emulsifiers as an oxygen-containing additive to mineral diesel fuels.

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