RU2327732C1 - Method obtaining high-octane motor car fuel - Google Patents

Abstract

FIELD: obtaining liquid hydrocarbon fuel.

SUBSTANCE: description is given of the method of obtaining high octane motor car fuel, which is achieved by putting into a mixer, in streamline conditions (Re= 1000÷1200) and heated up to 50÷70°C, straight-run gasoline or A-76 petrol with ethanol at concentration of 92-96%, with ratio of the alcohol to the petrol ranging from 55:45% vol. to 70:30% vol. and mixing them as the stream passes through the mixer at Re= 1000÷1200. Temperature in the mixer is 50-70°C and the mixer is full for a period of 20÷30 minutes. Light A-76 petrol can be used with boiling range of 42-155°C or light straight-run petrol with boiling range of 42-150°C.

EFFECT: obtaining of high octane motor car fuel with improved characteristics.

3 cl, 1 dwg 3 tbl

Description

The invention relates to the field of oil refining and petrochemicals, in particular to a technology for producing high-octane automobile fuels containing oxygenates.

The production of commercial fuels is usually carried out by mixing the products of oil refining processes and various additives (antiknock, oxygenates, antioxidants, etc.) that improve their operational characteristics.

Until now, metal-containing additives (additives) are most widely used as antiknock agents. As a result of the use of such additives, road transport accounts for almost half of all harmful emissions into the atmosphere.

One of the solutions to the problem of reducing harmful emissions is to develop a technology for producing more environmentally friendly high-octane fuel (hereinafter referred to as fuel) with the replacement or limitation of the use of harmful additives. It is proposed to use organometallic compounds, for example ferrocene and its derivatives, aromatic amines, for example N-methylaniline, and their mixtures, oxygenates (AManilov. Additives and additives. Improvement in the production of fuel, it is proposed to use individually or in a mixture (to obtain a synergistic antiknock effect) environmental characteristics of petroleum fuels. M: Chemistry, 1996, p.102-108).

A known method of producing automobile gasolines by mixing straight-run gasoline or A-76 gasoline with a multicomponent additive containing N-methylaniline, antioxidant, ferrocene, aniline, detergent additive "Automag" and aliphatic C ₁ -C ₅ -alcohols normal or branched, or mixtures thereof, and / or ethers of the formula ROR ¹ , where R = C ₁ -C _{3 is} primary or secondary, R ¹ = C ₃ -C _{5 is} straight or branched alkyl, or mixtures thereof (RU Patent No. 2132359, IPC 6 C10L 1/18, 1/22, publ. 06/27/99).

The disadvantages of these methods are due to the complexity of the preparation of the additive, the scarcity and high cost of such additives and fuel with their use, as well as the disadvantages of each component of this additive.

The disadvantages of using, for example, ferrocene in the production of fuels are poor solubility in the fuel and low stability of solutions due to the tendency of ferrocene to oxidize, which leads to a relatively short shelf life of both the additive and the resulting fuel due to the precipitation of oxidation products (precipitation of products oxidation). In addition, deposits of iron oxides are formed in the combustion chamber, which leads to interruptions in engine operation. To this we must add the scarcity of ferrocene, therefore, despite the well-known since the 40s of the XX century, its high efficiency on an industrial scale ferrocene has not been used.

The use of additives of aromatic amines, for example N-methylaniline, and their mixtures in the production of automobile fuels, increases the resin formation on the parts of the cylinder-piston group, which increases their wear and does not contribute to a decrease in the emission of nitrogen oxides (NO _x ) in the exhaust. These disadvantages limit the amount of additives used in the fuel, therefore, the increase in the octane number is relatively low. In addition, since 2005, the concentration of aromatic compounds is limited for environmental reasons.

The use of oxygen-containing compounds, which include low molecular weight alcohols (methanol, ethanol, etc.), ethers (for example, methyl tert.-butyl ether) and their mixtures, improves combustion characteristics, which significantly reduces harmful emissions, increases engine life, increases octane fuel. At the same time, the presence of lower alcohols in the composition of gasoline additives reduces the calorific value, leads to the depletion of the fuel-air mixture, and the use of ethers with poor biodegradability leads to their seepage into groundwater and environmental degradation.

At the same time, the production of fuel compositions based on gasoline and oxygenates, for example lower alcohols (methanol and ethanol), due to significant environmental advantages and the possibility of using renewable raw materials as one of the fuel components, is, despite some disadvantages, a promising direction in the development of technology for producing high-octane automobile fuels .

A known method for producing high-octane gasoline is that the straight-run gasoline fraction NK - 160 ° C is subjected to hydrotreating and then fractionated to obtain fractions NK - 85 ° C and 85 ° C - KK, the fraction NK - 85 ° C is isomerized to form iso -merizate, and the fraction of 85 ° C - CC is subjected to catalytic reforming, then 10-60 wt.% of gasoline of catalytic reforming is fractionated to obtain fractions of NK-85 ° C, 85-140 ° C, 140-200 ° C, 200 ° C - KK and to obtain the target product, the separated fractions are mixed with isomerizate in certain ratios. To reduce the proportion of highly aromatized components in this method, it is proposed to additionally introduce certain amounts of alkylbenzene, and / or straight-run fraction NK-85 ° C, and / or catalytic cracking gasoline, and / or up to 15% ethers of C ₁ -C ₅ alcohols or mixtures thereof with lower alcohols C ₁ -C ₄ . Without the addition of ethyl fluid, only A-76 and AI-80 gasolines can be obtained (RF patent No. 2153523, MKI C10L 1/04, C10G 69/08, 07.27.2000).

The disadvantages of this method are multi-stage, a relatively small increase in the octane number and a relatively low decrease in the proportion of aromatic hydrocarbons, including benzene.

The main disadvantage of known fuels with a certain content of methanol and ethanol is phase instability when water enters (for example, from moist air). During storage and transportation, fuel containing ethanol absorbs water. In this case, the phase stability of the fuel is violated, a water-alcohol layer is formed at the bottom of the tank, the alcohol content in the fuel is reduced, which impedes the operation of internal combustion engines, leads to a decrease in the octane number and corrosion of the equipment. Therefore, the use of fuel obtained with the addition of lower alcohols in low concentrations requires the mandatory inclusion of stabilizing additives in its composition, allowing homogenizing this system.

A known method of obtaining a composition of motor fuel by mixing gasoline components, aromatic component, nitroaromatic additives, ethers and / or aliphatic alcohols C ₁ -C ₅ (not more than 20%), and the mixture is carried out by circulation-acoustic mixing of the final mixture of components when generated in the compounding unit acoustic vibrations in the frequency range from 12 Hz to 30 kHz (RU, patent No. 2214444, IPC 7 C10L 1/06, C10L 1/18, publ. 20.10.2003).

The disadvantages of the method are the complexity of the production technology, due to the multicomponent nature of the mixture, the duration of its circulation and acoustic treatment, the use of special equipment, as well as relatively high concentrations of aromatic compounds, which are carcinogens and blood poisons.

A known method of producing high-octane automobile fuel by mixing straight-run gasoline or A-76 gasoline and ethyl alcohol at a concentration of 92-96% in a ratio of 75-85 vol.% And 15-25 vol.% Or 15-25 vol.% And 75-85 vol. %, respectively, by heating the resulting mixture to 40-90 ° C, followed by exposure at this temperature for 20-30 minutes, followed by cooling and re-heating to the same temperature and holding for 10-15 minutes (RU Patent No. 2246526, C10L 1 / 18, published on 02.20.2005).

The disadvantages of this method are the low phase stability of the resulting fuel and its deterioration during prolonged storage, especially at low temperatures, insufficient increase in the detonation resistance (octane number) in real operating conditions.

The objective of the invention is to develop a continuous process for the production of environmentally friendly automotive fuels based on gasoline and alcohol, which has increased detonation resistance in real conditions, exhibiting high phase stability during long-term storage and transportation, especially at low temperatures, while maintaining a relatively high calorific value.

The problem is solved by a method of producing high-octane automobile fuel, including mixing the original straight-run gasoline or A-76 gasoline with ethanol of a concentration of 92-96%. Moreover, the components are taken in the ratio of alcohol: gasoline from 55:45 vol.% To 70:30 vol.%, Before being fed into the mixer, the fuel components are heated to a temperature of 50 ÷ 70 ° C, the components are fed into the mixer, in which the same temperature is maintained, carried out in laminar mode at Re = 1000 ÷ 1200 when the mixer volume is completely filled and when it passes through the mixture stream in the same laminar mode for 20 ÷ 30 minutes The method of producing fuel can be carried out using lightweight A-76 gasoline with boiling limits of 42-155 ° C or lightweight straight-run gasoline with boiling limits of 42-150 ° C.

Table 1 presents the characteristics of the components used. Tables 2, 3 show the test results of the fuel compositions obtained in accordance with the declared modes and ratios. The technological process for producing fuel is presented in the diagram.

We give an example implementation of the proposed method.

Example 1. Pre-heated to 50 ° C ethanol with a concentration of 92 vol.% From the raw material tank 1 and gasoline A-76 from the raw material tank 2 in a ratio of 55 vol.%: 45 vol.% (2.75 l / min: 2, 25 l / min) continuously in laminar mode (Re = 1000) is pumped 3 and 4 into a common mixer 5, which is a pipeline, completely filling its volume. In the mixer, the components are combined, mixing, into one laminar stream (Re = 1000), and ethanol is fed from above as a heavier component, after which the total stream in the same laminar mode is fed into a commodity tank 6. The mixer travels for 30 minutes.

The same laminar regime of different flows can be maintained, for example, by using different sections of the raw material pipes to supply components to the mixer, the diameter of one of them can be constant, and the diameter of the other can be varied using a diaphragm.

With Re greater than 1200, “slippage” and a decrease in the contact of component flows are possible. At Re less than 1000, the process is not technologically advanced.

The remaining examples were carried out analogously to example 1, changing the conditions in the claimed intervals of the method. Characteristics of the obtained target product are shown in tables 2, 3.

The studied characteristics of the raw materials and the resulting fuels were determined in accordance with the following GOSTs:

- cloud point GOST 5066-91 - fractional composition GOST 2177-82 - octane number GOST 511-82 - content of actual resins GOST 1567-97 - density GOST 3900-85

Tests conducted at OAO Tatnefteproduct.

The experimental data presented in the tables show that the proposed method for producing fuel based on gasoline and ethanol can reduce the cloud point of the fuel to -65 ° C while increasing the octane number to 90 or more according to the motor method.

Thus, the proposed method for producing high-octane automotive fuel contains a new set of essential features, namely: the supply of components in the ratio of alcohol: gasoline from 55:45 vol.% To 70:30 vol.%, Preheated to 50-70 ° C, mixing for 20 ÷ 30 minutes in laminar mode at Re = 1000 ÷ 1200 in the mixer provided that its volume is completely filled, which allows to increase phase stability and detonation resistance of the resulting fuel.

Table 1 Characteristics of the starting components (gasolines and ethanol) Samples The name of indicators Gasoline A-76 A-76 gasoline facilitated Straight run gasoline Lightweight straight run gasoline Ethanol 1. Density at 20 ° C, g / cm ³ 0.7237 0.7128 0.7143 0.7097 0.805 2. Detonation durability: - octane number by 73 72 55 54 75 ¹ motor method; - octane number by research 78 77 60 60 95 ² method 3. The fractional composition of the fuel component: - start temperature 42 42 41 42 76 distillation, ° C; - distillation temperature 10%, ° С; 61 61 71 61 77 - distillation temperature 50%, ° С; 95 95 110 95 77 - distillation temperature 85%, ° С; 155 155 150 150 77 - distillation temperature 90%, ° С; 163 - 152 - 78 - end of boiling, ° С; 182 155 165 150 78 - residue in the flask,% 1,0 1,0 1,0 1,0 1,0 - balance and losses,% 2.0 2.1 2.0 2.0 1,6 4. The concentration of actual resins, mg / 100 cm ³ 1,5 1.4 1,0 1,0 2.6 5. The content of solids Absent Absent Absent Absent Absent ¹ From the source gasoline, 85-86% vol.
² For ethyl alcohol, the determination of the octane number by the guest method is not entirely correct

table 2 The results of comparative tests of fuel compositions obtained by the proposed method (Re = 1200, t = 70 ° C, τ = 20 min) Fuel composition The ratio of alcohol: gasoline,% vol. FUEL INDICATORS Motor Octane The boundary of phase stability, ° C Duration of phase stability (at normal pressure) Calorific value, kJ / l (calculated) Ethanol - A-76 gasoline 0: 100 73 below -80 not standardized 34200 15:85 ¹ 81 5 ~ 2 months 31700 50:50 81 -25 2-3 months 29400 55:45 86 -35 > 3 months 29200 60:40 89 -40 > 6 months 28700 70:30 92 -67 > 6 months 27800 85:15 ¹ 78 below -80 ~ 2 months 26200 100: 0 75 ³ -114 ⁴
-36 not standardized
~ 2 months 24,200
28700 60:40 ⁵ 84 Ethanol - Lightweight A-76 Gasoline ² 0: 100 72 below -80 not standardized 34500 15:85 ¹ 82 6 ~ 2 months 32100 50:50 79 -25 2-3 months 30500 55:45 86 -34 > 3 months 29700 60:40 88 -41 > 6 months 29100 70:30 92 -66 > 6 months 28100 85:15 ¹ 76 below -80
-35 ~ 2 months
~ 2 months 26400
29100 60:40 ⁵ 85 Ethanol - straight run gasoline 0: 100 55 below -80 not standardized 37100 15:85 ¹ 80 31 ~ 2 months 34300 50:50 77 7 2-3 months 31400 55:45 85 -one > 3 months 30800 60:40 87 -5 > 6 months 29800 70:30 91 -25 > 6 months 29300 85:15 ¹ 78 -40
-one ~ 2 months
~ 2 months 26800
29800 60:40 ⁵ 82 Ethanol - straight-run light gasoline ² 0: 100 54 below -80 not standardized 37500 15:85 ¹ 77 25 ~ 2 months 34900 50:50 76 5 2-3 months 32300 55:45 83 -3 > 3 months 31800 60:40 86 -7 > 6 months 30200 70:30 92 -28 > 6 months 29800 85:15 ¹ 77 -32
0 ~ 2 months
~ 2 months 26900
30200 60:40 ⁵ 83 ¹ Components taken in the proportions of the prototype.
² 85-86% vol.
³ For ethanol, the determination of knock resistance by the guest method (without modification) is difficult and not entirely correct.
⁴ Reference temperature onset of crystallization of dehydrated ethanol.
⁵ Fuel obtained under the conditions of the prototype (t = 90 ° C, τ ₁ = 20 min, τ ₂ = 15 min).

Table 3 The results of comparative tests of fuel compositions obtained by the proposed method (Re = 1000, t = 50 ° C, τ = 30 min.) Fuel composition The ratio of alcohol: gasoline,% vol. FUEL INDICATORS Motor Octane The boundary of phase stability, ° C Duration of phase stability (at normal pressure) Calorific value kJ / l, (estimated) Ethanol - A-76 gasoline 0: 100 73 below -80 not ok 34200 15:85 ¹ 82 +5 ~ 2 months 31700 50:50 80 -26 2-3 months 29400 55:45 87 -35 > 3 months 29200 60:40 89 -41 > 6 months 28700 70:30 92 -66 > 6 months 27800 85:15 ¹ 77 below -80
-114 ⁴ ~ 2 months
not ok 26200
24,200 100: 0 75 ³ Ethanol - Lightweight A-76 Gasoline ² 0: 100 72 below -80 not standardized 34500 15:85 ¹ 81 +7 ~ 2 months 32100 50:50 79 -24 2-3 months 30500 55:45 86 -32 > 3 months 29700 60:40 87 -40 > 6 months 29100 70:30
85:15 ¹ 91
77 -65
below -80 > 6 months
~ 2 months 28100
26400 Ethanol - straight run gasoline 0: 100 55 below -80 not standardized 37100 15:85 ¹ 80 +32 ~ 2 months 34300 50:50 76 +7 2-3 months 31400 55:45 84 0 > 3 months 30800 60:40 86 -four > 6 months 29800 70:30
85:15 ¹ 91
78 -25
-40 > 6 months
~ 2 months 29300
26800 Ethanol - straight-run light gasoline ² 0: 100 54 below -80 not standardized 37500 15:85 ¹ 77 +26 ~ 2 months 34900 50:50 75 +5 2-3 months 32300 55:45 82 -3 > 3 months 31800 60:40 85 -6 > 6 months 30200 70:30
85:15 ¹ 92
77 -27
-32 > 6 months
~ 2 months 29800
26900 ¹ Components taken in the proportions of the prototype.
² 85 - 86% of volumetric gas was driven away from the source gasoline.
³ For ethanol, the determination of knock resistance by the guest method (without modification) is difficult and not entirely correct.
⁴ Reference temperature onset of crystallization of dehydrated ethanol.

Claims (3)

1. A method of producing high-octane automobile fuel, comprising mixing the initial straight-run gasoline or A-76 gasoline with ethanol of a concentration of 92-96%, characterized in that the components are taken in the ratio of alcohol: gasoline from 55:45 vol.% To 70:30 vol. .% before feeding into the mixer, the fuel components are heated to a temperature of 50 ÷ 70 ° C, the components are fed into the mixer, which maintain the same temperature, in laminar mode at Re = 1000 ÷ 1200 when the volume of the mixer is completely filled and when it passes through the mixture flow in the same laminarne ohm mode for 20 ÷ 30 min. 2. The method of producing high-octane automobile fuel according to claim 1, characterized in that lightweight A-76 gasoline is used with boiling limits of 42-155 ° C. 3. The method of producing high-octane automobile fuel according to claim 1, characterized in that lightweight straight-run gasoline with boiling limits of 42-150 ° C is used.