RU2524955C1 - Multifunctional hydrocarbon-containing fuel additive and fuel composition containing same - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a multifunctional hydrocarbon-containing fuel additive, which includes a mixture of one or more mixed ethers with one or more oxygenates, wherein the mixed ethers used are N-methyl-para-anisidine and/or N-methyl-para-phenetidine, the oxygenates used are dimethyl carbonate and/or diethyl carbonate, and/or methyl acetate, and/or ethyl acetate, and/or methylal. Disclosed additives enable maximum utilisation of substances contained therein, provide the required physical and chemical properties, the quality of additives themselves and fuel containing said additives. The invention also relates to a hydrocarbon-containing fuel composition which contains hydrocarbon fuel and said additive in amount of 0.01-30 wt % with respect to the weight of the fuel composition.

EFFECT: disclosed fuel composition has high antioxidation stability, improved environmental friendliness, antiknock rating, combustion efficiency, reduced soot formation and deposits on engine components.

4 cl, 1 tbl

Description

Technical field

The invention relates to petrochemistry, the oil refining industry, and in particular to the production of fuels for internal combustion engines, in particular gasoline and diesel fuel. The invention can be used to obtain multifunctional additives to hydrocarbon fuel, as well as in the production of hydrocarbon fuel compositions containing these additives.

The claimed multifunctional additives to hydrocarbon fuels (fuels) allow the use of its constituent substances with maximum efficiency, provide the required physico-chemical properties, the quality of the additives themselves and the fuels that contain them.

The substances that make up the inventive multifunctional additives have individual boiling points lying in a wide range of values, different elemental composition and effectiveness, which allows, by changing the ratio between the substances of the additive to regulate the fractional composition, oxygen and nitrogen in the composition of the additive and fuel, and also achieve the necessary characteristics of fuels during their production. In addition, by changing the quantitative content of the components of the additive (within the stated range of values), it is possible to control the physicochemical properties of the additives themselves, for example, to change the rheology, including to ensure the possibility of its transportation, storage and use in liquid form under various weather conditions, change the effectiveness of certain properties depending on the tasks.

State of the art

Currently, a limited number of substances are used as additives and additives to fuels, which have their advantages and disadvantages.

The prior art it is known to use N-methyl-para-anisidine as an anti-knock additive to motor fuel and a fuel composition containing it [RF Patent No. 2309944]. The advantage of using N-methyl-para-anisidine is the high additive efficiency, which provides an increase in the octane number of the fuel composition. The disadvantages are the high melting point (26-28 ° C) of the substance and the associated technological difficulties of entering into gasoline, the need for thorough mixing (compounding), difficulties in transporting, unloading, and storage of the additive with consumers.

It is known to use N-methyl-para-phenethidine as an antiknock additive to motor fuel and a fuel composition containing it [RF Patent No. 2309943]. The use of derivatives of para-ethoxyanilines increases the resistance of hydrocarbon fuels to detonation. The disadvantages include the need for thorough mixing (compounding), lower efficiency in increasing the octane number of gasolines compared to N-methyl-para-anisidine, lowering fluidity at low temperatures, difficulties in transportation, unloading, and storage of the additive at consumers.

It is known to use dimethyl carbonate and diethyl carbonate as oxygenates in reformed gasoline and high-octane components in the composition of the fuel composition. Advantages: Dimethyl carbonate contains more oxygen (53%) than MTBE (methyl tert-butyl ether) or TAME (tert-amyl methyl ether), has an octane number of about 130, a boiling point of no higher than 150 ° C, less volatile in comparison with MTBE and TAME [RF Patent No. 2367648, international application W02005 / 102986]. The disadvantages are the low efficiency of substances when used in fuel compositions to increase octane numbers and the associated need for their use in large quantities in gasolines.

The use of methyl acetate and ethyl acetate is known [US Patent No. 6923839]. The authors use methyl acetate and ethyl acetate to provide oxygen to the fuel and increase the octane number of gasolines. Disadvantages are also the low efficiency of substances when used in fuel compositions to increase octane numbers and the associated cost increase in the production of high-quality fuels.

The use of ethyl acetate as a fuel or fuel additive is known [Application for US invention No. 201010296744]. According to the invention, the fuel mixture contains a hydrocarbon-containing fuel component and ethyl acetate. As the hydrocarbon-containing fuel component, gasoline, diesel, bioethanol or biodiesel can be used. The disadvantages are the low efficiency of the substance when used in fuel compositions to increase octane numbers and the associated cost increase in the production of high-quality fuels. In addition, if an additive is used in biodiesel and bioethanol, additional use of antioxidants will be required, given their low oxidation stability.

The use of methyl acetate for the preparation of motor gasoline is known [RF Patent No. 2182163], while automobile gasoline can be used without changing the structure and parameters of the engine. The disadvantages listed when using ethyl acetate as a fuel additive to gasoline are also characteristic of this invention.

It is known to use methylal as a fuel additive in concentrations from 1-10% [Application for Chinese invention No. 105229298A]. Among the shortcomings, one can note the low boiling point of methylal, the volatility and weak antiknock activity, and, associated with this, the restriction on the introduction into the fuel.

It is known the use of mixed additives based on N-methylaniline [Patent for the invention of the Russian Federation No. 2155793], consisting of N-methylaniline - 6.5-70; tertiary butyl alcohol - 0.2-27; detergent additives - not more than 6; ether of acetic acid and fusel oil - 0.1-25; methyl tert-butyl ether up to 100%. The disadvantage of this additive is the high toxicity of N-methylaniline, lower efficiency in increasing the octane number of gasolines compared to N-methyl-para-anisidine, as well as the need to use additional components that stabilize N-methylaniline and fuel from oxidation, the introduction of additional detergent components in fuel.

Considering the unique properties of N-methyl-para-anisidine and N-methyl-para-phenethidine, which are simple mixed ethers, their use as additives to gasolines in order to increase the octane number (increase the detonation properties of fuels) is very promising. However, in the case of their application, in addition to the indicated property, it becomes necessary to obtain fuels additionally characterized by antioxidant protection, a certain oxygen content, fractional composition, etc. In addition, due to the growing requirements for fuels, the requirements for added additives are also growing. In this regard, the development of mixed additives with multifunctional action, solving the problem of obtaining high-quality fuels, is very relevant.

Closest to the claimed solution are inventions according to patents of the Russian Federation No. 2309944; RF №2309943 regarding the use of N-methyl-para-anisidine and N-methyl-para-phenetidine in combination with oxygenates, which are used as MTBE, ETBE, TAME, methyl, ethyl, butyl alcohols. However, our comprehensive studies of these mixed formulations showed that N-methyl-para-anisidine and N-methyl-para-phenetidine have different solubilities in these oxygenates, affect the temperature of their crystallization and their precipitation at low temperatures from the composition of the additive. Also, each of the oxygenates to varying degrees affects the individual characteristics of gasolines, antiknock efficiency, oxygen content, boiling point, which is very important in conditions of large-tonnage gasoline production. Also, the proposed oxygenates have limitations on their use. In addition, the effectiveness of these mixed formulations is shown on gasolines.

The presence of a large number of published technical solutions regarding the composition of mixed fuel additives suggests that the development of each is an individual task for each compound and for each type of fuel.

The use of the declared additives allows you to choose the optimal mixed composition of the additive for any production of fuels with a minimum number of components.

To date, there is no information in the literature on the use of N-methyl-para-anisidine and / or N-methyl-para-phenetidine in combination with dimethyl carbonate and / or diethyl carbonate and / or methyl acetate and / or ethyl acetate, and / or methylal and the properties of fuels obtained with their use.

Disclosure of invention

The present invention is the creation of a comprehensive multifunctional fuel additives to improve its properties.

The technical result consists in obtaining fuel compositions characterized by the following parameters: high antioxidant stability, high environmental friendliness, detonation resistance (to gasoline), full combustion, low carbon formation and deposits on engine parts. The use of the declared additives has a good prospect for use in both modern and promising internal combustion engines, which are designed taking into account the growing environmental requirements and resource savings.

The technical result is achieved by creating a complex, multifunctional additive to hydrocarbon-containing fuel, including a mixture of one or more simple mixed ethers with one or more oxygenates, characterized in that N-methyl-para-anisidine and / or N- are used as simple mixed ethers methyl para-phenethidine, dimethyl carbonate and / or diethyl carbonate and / or methyl acetate and / or ethyl acetate and / or methylal are used as oxygenates.

A particular embodiment of the present invention is the aforementioned additive, characterized in that the simple, mixed ethers and oxygenates are taken in the following amounts:

Simple mixed ethers - 0.1-99.9% of the mass.

Oxygenates - 0.1-99.9% of the mass.

Another particular embodiment of the present invention is the aforementioned additive, characterized in that it further comprises components that reduce the limiting temperature of the filterability and / or anti-wear and / or detergent properties.

Also, the problem is solved by developing a hydrocarbon-containing fuel composition comprising a hydrocarbon-containing fuel and the aforementioned additive, where the specified additive is contained in an amount of from 0.01 to 30% of the mass. in relation to the weight of hydrocarbon fuel.

The inventors have discovered that an additive consisting of a mixture of N-methyl-para-anisidine and / or N-methyl-para-phenetidine and dimethyl carbonate and / or diethyl carbonate and / or methyl acetate and / or ethyl acetate and / or methylal, or their combinations, allows to reduce the crystallization temperature and viscosity, which facilitates the pumpability of the additive during its loading and unloading, facilitates the process of introduction into hydrocarbon fuel, and also provides a significant increase in the stability of fuels from oxidation (when using the claimed mixed ext wok noted sharp decrease oxidative processes in fuels, including increased the induction period of various gasolines, fuel fractions and components), increasing the octane number of gasoline, provides the necessary oxygen content facilitates engine start at low temperatures. The invention allows to create hydrocarbon fuels that meet the highest modern requirements, taking into account toughening requirements for environmental friendliness and economy, and these are higher compression ratios, requirements for octane and cetane numbers of fuels to ensure their completeness of combustion, to achieve maximum efficiency.

The introduction of a multifunctional additive in the fuel improves the antioxidant properties and / or antiknock and / or physicochemical properties of the fuels and / or the completeness of combustion and / or the reduction of carbon formation and / or the reduction of deposits allows increasing the volume of fuel produced and also provide the necessary oxygen content in the fuel composition.

Also adding these complex additives in an amount of from 0.01 to 30% of the mass. in hydrocarbon fuel provides antioxidant protection of fuels, even if these fuels contain a significant amount of unsaturated hydrocarbons. At the same time, when an additive is added to the base gasoline, the necessary oxygen content is provided, the antiknock properties are increased, the fuels are protected from oxidation, as well as the reduction of harmful emissions of CO, CH, NOx, CO ₂ , and benzpyrenes. Depending on the oxygenates used, it is possible to effectively control the fractional composition of gasolines. When this additive is introduced into diesel fuel, engine starting at low temperatures is greatly facilitated, the process of fuel combustion is improved, and harmful emissions are reduced. In all cases, the introduction of additives significantly increases the volume of production of commercial fuels, which gives the right to consider that this additive is a full-fledged component of modern fuels.

The invention is illustrated by the following examples.

1. Assessment of the effect of additives on antioxidant ability. The induction period was evaluated in accordance with GOST R EN ISO 7536 at a temperature of 100 ° C and an initial oxygen pressure of about 700 kPa. The research results are carried out in table. one.

These examples show that additives reliably show their effectiveness in concentrations starting from 0.01% of the mass. in relation to fuels.

The table shows that the induction period of fractions with a high content of unsaturated hydrocarbons increased significantly with the introduction of additives with 0.01% of the mass. in relation to fuel.

Analysis of the use of the declared additives in fuels in order to increase stability from oxidation showed the advisability of using the additive in a concentration from 0.01 to 5%. In this interval, there is a sufficient stabilization of all possible (used) fractions (components) of hydrocarbon fuels. In addition, it was noted that the antioxidant effect of the additive is enhanced with a higher content of N-methyl-4-methoxyaniline and / or N-methyl-4-methoxyaniline with respect to the claimed oxygenates.

Table 1 Name of gasoline component Name of additive Induction period, min The concentration of additives,% mass 0 0.01 0.05 0.1 0.2 0.25 0.4 one 5,0 Commodity AI 92 gasoline - 900 - N-methyl-4-methoxyaniline / methyl acetate (90% / 10%) > 1000 > 3000 - N-methyl-4-methoxyaniline / ethyl acetate (10% / 90%) > 1000 > 3000 - N-methyl-4-methoxyaniline / dimethyl carbonate (80% / 20%) > 1000 > 3000 - N-methyl-4-methoxyaniline / dimethyl carbonate (0.01% / 99.99%) 920 > 1000 > 3000 Polymer gasoline 630 - N-methyl-4-methoxyaniline / methyl acetate (10% / 90%) 900 > 1000 > 3000 - N-methyl-4-methoxyaniline / methylal (7% / 93%) 870 > 1000 > 3000 - N-methyl-4-methoxyaniline / diethyl carbonate (10% / 90%) 930 > 1000 > 3000 Catalytic Cracking Gasoline (BCC) 210 - N-methyl-4-methoxyaniline / methyl acetate (90% / 10%) 280 320 410 > 1000 > 3000 - N-methyl-4-methoxyaniline / mtilal (90% / 10%) 290 > 1000 > 3000 - N-methyl-4-methoxyaniline / ethyl acetate (90% / 10%) 300 > 1000 > 3000 N-methyl-4-methoxyaniline / dimethyl carbonate (90% / 10%) 322 > 3000 Coking gasoline 175 > 3000 - N-methyl-4-methoxyaniline / methyl acetate (0.01% / 99.99%) 200 360 > 1000 > 3000 - N-methyl-4-methoxyaniline / methyl acetate (90% / 10%) 195 400 > 1000 > 3000 - N-methyl-4-methoxyaniline / ethyl acetate 180 > 3000 N-methyl-4-methoxyaniline / diethyl carbonate (90% / 10%) 200 > 1000 > 3000

2. Another confirmation of the versatility of the additives of the present invention are examples of a significant reduction in the toxicity of exhaust gases of gasoline and diesel engines. Given the fact that all of the proposed compounds are substances with a high oxygen content (oxygen in the composition of the ether groups), their introduction into gasolines in certain concentrations increases the completeness of fuel combustion, thereby reducing emissions of the most harmful compounds, such as NO, CH, CO CO ₂ , unburned hydrocarbons (soot), benzpyrenes. At the same time, in order to ensure optimal combustion conditions, it is necessary to observe the oxygen content in fuels recommended by engine developers. The oxygenates claimed in the present invention contain a large proportion of oxygen (this indicator is higher than that of conventionally used additives MTBE, TAME, ETBE), thus even their small content in the fuel can significantly increase the proportion of oxygen. The use of a complex additive with the use of highly effective substances N-methyl-para-anisidine and / or N-methyl-para-phenetidine to increase the octane number allows for the optimal oxygen content and maximum increase in the octane number at low concentrations.

With existing technologies for the production of fuels, the most effective ratios of N-methyl-para-anisidine and / or N-methyl-para-phenetidine with oxygenates are 0.01-30 / 99.99-70% of the mass and content in the fuel of 0.01-30 %, the recommended concentration for increasing the octane number from 0.1 to 10% of the mass. It should be borne in mind that with toughening environmental standards and increasing the efficiency of hydrocarbon engines, they will inevitably require an increase in the degree of compression of fuels, and therefore, an increase in the requirements for the detonation resistance (increase in the octane number) of gasolines, and this parameter becomes one of the determining ones, and the recommended ratios of the components of the additive can significantly change to the extreme values suggested.

Particular examples of the effectiveness of the claimed additives:

• Using additives in a ratio of 10% of the mass. N-methyl-para-anisidine and 90% of the mass. methyl acetate was obtained AI 95 gasoline at a concentration of 6% of the mass, emission of harmful emissions decreased on average by 10-15%, had an induction period> 3000 min.

• The introduction of a similar additive in diesel fuel at a concentration of 15% led to a reduction in the emission of harmful emissions by 15-20%.

• Studies on the effect of the declared additives at low temperatures have shown that the most optimal ratios of N-methyl-para-anisidine and / or N-methyl-para-phenetidine to oxygenates are 0.01-30 / 99.99-70, respectively, and Recommended for use in cold climates. N-methyl-para-anisidine and / or N-methyl-para-phenethidine remain in a liquid state, which facilitates transportation, storage and introduction into the fuel. For example, an additive containing up to 15% N-methyl-para-anisidine and / or N-methyl-para-phenethidine and the rest dimethyl carbonate and / or diethyl carbonate and / or methyl acetate and / or ethyl acetate and / or methylal, or combination, had good stability and did not drop out at low temperatures.

• With the introduction of additives containing 0.01% of the mass. N-methyl-para-anisidine and / or N-methyl-para-phenethidine and 99.99% dimethyl carbonate and / or diethyl carbonate and / or methyl acetate and / or ethyl acetate and / or methylal in gasoline of 5 wt% were obtained in the average increase in the octane number by 2-3 units, depending on the initial octane number.

• With the introduction of an additive containing 10% by weight of N-methyl-para-anisidine and / or N-methyl-para-phenethidine and 90% dimethyl carbonate and / or diethyl carbonate and / or methyl acetate and / or ethyl acetate and / or methylal in gasoline 5% of the mass received an average increase in octane by 4-5 units, depending on the initial octane number.

• With the introduction of an additive containing 99.99% by weight of N-methyl-para-anisidine and / or N-methyl-para-phenetidine and 0.01% dimethyl carbonate and / or diethyl carbonate and / or methyl acetate and / or ethyl acetate, and / or methyl in gasoline 1% of the mass. received an average octane increase of 3-6 units, depending on the initial octane number of fuel.

3. In regions with a hot climate, the optimal use of additives in the ratios of 50-99.99% of the mass of N-methyl-para-anisidine and / or N-methyl-para-phenetidine and 0.01-50% of the mass. oxygenates due to the fact that oxygenates are more boiling and volatile compounds, as well as fuels under these conditions are more susceptible to oxidation. The introduction of additives is more appropriate in concentrations from 0.01-5%. Additives under these conditions also remain in a liquid state, which facilitates transportation, storage and their introduction into the fuel.

Claims (4)

1. A multifunctional additive to hydrocarbon-containing fuel, comprising a mixture of one or more mixed ethers with one or more oxygenates, characterized in that N-methyl-para-anisidine and / or N-methyl-para-phenethidine are used as simple mixed ethers , dimethyl carbonate and / or diethyl carbonate and / or methyl acetate and / or ethyl acetate and / or methylal are used as oxygenates. 2. The additive according to claim 1, characterized in that the simple, mixed ethers and oxygenates are taken in the following amounts:
Simple mixed ethers - 0.1-99.9 wt.%
Oxygenates - 0.1-99.9 wt.% 3. The additive according to claim 1, characterized in that it additionally contains components that reduce the limiting temperature of filterability, and / or anti-wear, and / or washing properties. 4. The hydrocarbon-containing fuel composition comprising a hydrocarbon-containing fuel and the additive according to claim 1, where said additive is contained in an amount of from 0.01 to 30 wt.% With respect to the weight of the hydrocarbon-containing fuel.