RU2307151C1 - Motor gasoline additive - Google Patents

Abstract

FIELD: petroleum processing and petrochemical industry.

SUBSTANCE: additive contains 0.5-10% methanol or methanol-ether fraction, 1-50% cosolvent, 0.1-1% corrosion inhibitor represented by complex salts of alkylamines with saturated or unsaturated mono- or dicarboxylic acids of general formula [HN(R)(R₁)(R₂)]⁺[R₃(COO)]^-, where R, R₁, and R₂ represent H, CH₃, C₂H₅, or C₂H₄OH; R₃ represents saturated or unsaturated olefin or isoparaffin novel hydrocarbon radical containing 8 to 30 C atoms; or R₄COOH, where R₄ represents hydrocarbon radical having 4-18 C atoms; the rest being watered ethyl alcohol. Above-mentioned cosolvent can be a substance selected from the group consisting of isopropyl alcohol, isobutyl alcohol, butyl alcohol production by-product, fusel oil, and mixture thereof. Corrosion inhibitor can be, for example, selected from complex salts of triethylamine, diethanolamine and C₁₀-C₁₈-fatty acids, oil acids, vegetable oil acids, and the like.

EFFECT: increased antiknock efficiency of additive, increased stability of fuel al low temperatures, lack of corrosion of metals, and satisfaction of requirements of state standard concerning liquid alcohol-containing fuels for spark-plug ignition engines.

2 cl, 2 tbl, 5 ex

Description

The invention relates to the field of oil refining and petrochemicals, in particular, to an additive to gasoline.

Currently, due to the need to solve environmental problems, the development of additives that increase the octane number of gasoline and reduce emissions of harmful substances from exhaust gases is an urgent task.

Ethanol, which simultaneously reduces the content of harmful impurities of carbon monoxide CO and unburned hydrocarbons CH in the exhaust gases (OG) of automobiles, is widely known as an octane enhancing additive. However, it should be noted that when ethanol (usually watered) is added to motor gasoline, the main disadvantage of the resulting gas-alcohol mixtures is phase instability, i.e., delamination at low temperatures. The addition of alcohol also leads to an increase in the corrosiveness of gas-alcohol mixtures with respect to metals.

Car gasoline additives are known which, along with ethanol, contain components such as aromatic amines and organometallic compounds.

For example, in RF patent No. 2129141, C10L 1/18, 1999, the composition of the additive based on stabilized ethyl alcohol containing 5-10 wt.% N-methylaniline and 0.05-0.15% ferrocene and / or its derivative is claimed. In the patent of the Russian Federation No. 2161639, С10L 1/18, 2001, the composition of the additive based on ethyl alcohol includes 6-20 wt.% Aromatic amine, 0.1-4 wt.% Organometallic additives (methylcyclopentadienyl-tricarbonyl manganese or dicyclopentadienyl iron derivative), in addition , 0.1-1.5 wt.% Crotonic aldehyde and 0.2-2.0 wt.% Acetic aldehyde.

The main disadvantage of additives containing aromatic amines is their aggressiveness with respect to rubbers, low chemical stability, especially in the presence of lower alcohols, and consequently the tendency to form deposits on engine elements, as well as their pungent odor. A drawback of additives to motor gasolines containing organometallic compounds based on manganese and iron is that these compounds form solid oxides of manganese and iron during fuel combustion, which can lead to increased wear of engine parts and negatively affect the operation of spark plugs.

Known multifunctional additive to motor gasoline based on ethyl alcohol, which contains the following components, wt.%:

N-methylaniline 6.0-12.0 co-solvent 0.2-20 amide based detergent 0.5-1.5 ethanol up to 100

(Eurasian patent No. 000882, C10L 1/18, 2000).

As a stabilizer to lower the cloud point of a gas-alcohol mixture, C ₃ -C ₅ alcohols are used.

The additive may additionally contain 0.2-0.4 wt.% Anticorrosive component and 0.01-0.1 wt.% Antioxidant.

The disadvantage of this additive is that it contains N-methylaniline, which, as mentioned above, has aggressiveness with respect to rubbers, low chemical stability, especially in the presence of lower alcohols, and, as a result, a tendency to form deposits on engine elements.

Ethanol-based octano-enhancing additives are also known, which do not include aromatic amines and organometallic compounds.

For example, an additive to motor gasolines based on ethyl alcohol and alkyl acetate with C ₁ -C ₆ alkyl radicals of a linear and branched structure is known. When added to gasoline, alkyl acetate in a concentration of 0.1-1 wt.% Improves the stability of the fuel composition (US Pat. US No. 4394133, C10L 1/18, 1983).

A motor fuel additive is also known, containing hydrated ethyl alcohol and a co-solvent, which are C ₃ -C ₅ higher aliphatic alcohols, for example propyl, isopropyl alcohol, butyl, isobutyl and tert-butyl alcohol, amyl and isoamyl alcohol, or mixtures thereof (US Pat. No. 4541836, C10L 1/18, 1980).

The fuel composition containing this additive has the following composition, wt.%:

watered ethyl alcohol 1-12 aliphatic alcohols C ₅ -C ₅ 0.3-4 petrol up to 100

The disadvantage of fuel compositions containing these additives is that they exhibit corrosiveness to metals.

The closest in composition to the claimed is an additive to gasoline based on flooded ethyl alcohol, containing waste hydrolysis production of ethyl alcohol from wood raw materials (8-80 wt.%) As a co-solvent and ethyl alcohol (up to 100 wt.%), Which is added to gasoline in an amount of 2-20 wt.% (US Pat. RF No. 2068871, C10L 1/02, C10L 1/18, 1996).

The so-called "aldehyde-ether-alcohol fraction", which includes C ₃ -C ₅ aliphatic alcohols, esters of methyl and ethyl alcohols and formic and acetic acids, furfural and other organic compounds, is used as waste from the production of ethyl alcohol from wood raw materials.

The disadvantage of the additive is that it does not sufficiently increase the octane number of gasoline, provides insufficient phase stability of the fuel and, when introduced into the fuel, is highly corrosive to metals.

The objective of the invention is the development of a high-octane ash-free additive for gasoline based on ethyl alcohol, which provides fuel stability at low temperatures and does not have increased aggressiveness with respect to metals.

To solve this problem, we propose an additive to water gasoline based on flooded ethyl alcohol, including a co-solvent, which is characterized in that it additionally contains methanol or a methanol-ether fraction and a corrosion inhibitor, which is a complex salt of alkyl amines and saturated or unsaturated mono- or dicarboxylic acids with a total formulas:

[HN (R) (R ₁ ) (R ₂ )] ⁺ [R ₃ (COO)] ^- ,

where R, R ₁ , R ₂ is —H, —CH ₃ , —C ₂ H ₅ , —C ₂ H ₄ OH;

R ₃ is a saturated or unsaturated olefin or isoparaffin hydrocarbon radical containing from 8 to 30 C atoms;

or R ₄ COOH, where R _{4 is a} hydrocarbon radical containing 4-18 C atoms,

in the following ratio of components, wt.% .:

methanol or methanol-ether fraction 0.5-10 co-solvent 1,0-50 corrosion inhibitor 0.1-1 watered ethyl alcohol the rest is up to 100

The co-solvent additive contains a substance selected from the group: isopropanol, isobutanol, a by-product of the production of butyl alcohols, fusel oil, or a mixture thereof. It should be noted that the co-solvent simultaneously acts as a stabilizer.

As a corrosion inhibitor related to complex salts of alkyl amines and saturated or unsaturated mono- or dicarboxylic acids, for example, complex compounds of triethylamine, diethanolamine and C ₁₀ -C ₁₈ fatty acids, petroleum acids, vegetable oils, and others can be used.

The additive is introduced into motor gasoline in an amount of 3-15 wt.%. The following products are used to prepare the proposed automotive gasoline additive:

- alcohols (with a water content of 0.5 to 5.4 wt.%) are used as water-diluted ethyl alcohol - synthetic denatured according to TU 2421-072-05766563-2003, rectified hydrolysis technical denatured according to TU 2421-003-32465440-99 or TU 2421-068-05766563-2001;

- methanol according to GOST 2222-95 or methanol-ether fraction of ethyl alcohol production containing up to 80 wt.% methanol, C ₂ -C ₅ alcohols, ethers and esters of C ₁ -C ₅ alcohols, etc.

- isopropanol according to GOST 9805;

- technical isobutanol in accordance with GOST 9536;

- a by-product of the production of butyl alcohols (butyl-butanol formate fraction), which is a mixture of C ₁ -C ₈ alcohols, aldehydes, ethers and esters, with the main content being C ₄ alcohols (isobutanol and n-butanol);

- “fusel oil” - according to GOST 17071, which is a mixture of alcohols: amyl, isobutyl, n-propyl, ethyl, water and a small amount of other organic compounds. The waste is obtained in the process of rectification of ethyl alcohol;

- as a corrosion inhibitor related to complex salts of alkyl amines and saturated or unsaturated mono- or dicarboxylic acids, the anti-corrosion additive INCOR, manufactured in accordance with TU 0257-005-11475232-2005, or the complex compound of diethanolamine and C ₁₀ -C fatty acids can be used ₁₈ , and other compounds from this class.

The gasoline additive according to this invention is prepared using standard equipment by mixing the components until a homogeneous solution is obtained.

The antiknock efficiency of the proposed additive was evaluated by introducing it into the base fuel (OCHI 70). Detonation testing of samples of fuel compositions containing the proposed additive was carried out according to GOST 8226 research method.

Assessment of the low-temperature properties of the samples of the proposed additives with gasoline was carried out according to GOST 5066-56. According to the requirements of GOST R 52201 "Benzanols", the cloud point of gasoline of summer type should not be higher than minus 10 ° C, and winter type should not be higher than minus 30 ° C.

Evaluation of the anti-corrosion properties was carried out according to ASTM D665. In accordance with GOST R 52201 "Benzanols" corrosion of a steel rod should not exceed 1 point.

To illustrate the claimed technical solution, 5 samples of additives of various compositions were prepared, which in the amount of 3-15 wt.% Were introduced into the base fuel (OCH 70).

The composition of the samples of the proposed additives are given in table 1.

The test results of the proposed additives are given in table.2.

The test results shown in table 2 showed that when the prepared samples of the proposed additive are introduced into the base fuel (OCHI 70), the octane number is increased by the research method (Δ OCHI) by 3-8 units. In this case, the cloud point of the base fuel with the proposed additive is from minus 18 to minus 41 ° C, the corrosion of the steel rod is 0-1 points according to ASTM D665, which meets the requirements of GOST R 52201 "Benzanols" on liquid alcohol-containing motor fuels for spark ignition engines .

Thus, the proposed additive to motor gasoline at the claimed ratio of components has a high antiknock efficiency, provides fuel stability at low temperatures and does not cause corrosion with respect to metals.

Table 1 The composition of the samples of the proposed additives to gasoline Name of components The content of components in the additive sample, wt.% one 2 3 four 5 Methanol
Methanol ether fraction 1,0 -
5,0 0.5 3.0 -
10 Co-solvent: Isopropanol 35 twenty Isobutanol - one - twenty Production waste thirty - - - 5 butyl alcohol "fusel oil" - - - 40 5 Corrosion inhibitor: INCOR 0.1 0.8 1,0 Complex compound of diethanolamine and fatty acids C ₁₀ -C ₁₈ - one - 0.5 - Watered Ethyl Alcohol Up to 100 Up to 100 Up to 100 Up to 100 Up to 100

table 2 Test results for gasoline with the proposed additive No. p / p Additive Test Number and Test Indicators The additive content in gasoline, wt.% And test results one 2 3 four 5 one Sample 1 fifteen 2 Sample 2 5 3 Sample 3 8 four Sample 4 10 5 Sample 5 3 Indicators one Octane gain Research Method Numbers (Δ GPI) 7.9 4.0 7.3 7.5 2.9 2 Cloud point, ° С Minus 30 Minus 25 Minus 18 Minus 36 Minus 41 3 Steel Rod Corrosion, ASTM D665 Scores one 0 0 one 0

Claims (2)

1. An additive to water gasoline based on water-saturated ethanol, including a co-solvent, characterized in that it further comprises a methanol or methanol-ether fraction and a corrosion inhibitor, which is a complex salt of alkyl amines and saturated or unsaturated mono- or dicarboxylic acids of the general formula [HN (R) (R ₁ ) (R ₂ )] ⁺ [R ₃ (COO)] ^- , where R, R ₁ , R ₂ is —H, —CH ₃ , —C ₂ H ₅ , —C ₂ H ₄ OH; R ₃ is a saturated or unsaturated olefin or isoparaffin hydrocarbon radical containing from 8 to 30 C atoms or R ₄ COOH, where R _{4 is a} hydrocarbon radical containing 4-18 C atoms, in the following ratio, wt.%: methanol or methanol-ether fraction 0.5-10 co-solvent 1,0-50 corrosion inhibitor 0.1-1 watered ethyl alcohol the rest is up to 100 2. The additive according to claim 1, characterized in that as a co-solvent contains a substance selected from the group: isopropanol, isobutanol, a by-product of the production of butyl alcohols, fusel oil, or a mixture thereof.