LT5161B - Additive for fuels on the basis of improved ethanol - Google Patents

Abstract

The present invention provides a fuel additive on a basis of improved bioethanol; said additive reduces amount of of damage materials in fuel combustion products. The fuel additive has a combustion catalyst consisting of mixture of 0,001 to 0,5 % byweight of iron(III) acetylacetonate and copper(II) organic compound in ratio of 80-90:10-20. Suitable copper compound may be copper naphtenate, copper organic inner compound salt in alkylaminoalkylketone derivatives form, copper acetylacetonate andcopper chelate compound on the basis of product of condensation of acetoacetylferrocene with ethylenediamine. The bioethanol is prepared from stocks of food such as sugar-beet which is refined by rectification. Said bioethanol may have additional fraction of ethers and aldehydes and/or fusel oil, and no less than 0,02 % by weight of tetraethoxysilane without impurities of hydrolysis.

Description

The present invention relates to the processing, modification and production of motor fuels with improved environmental performance; in particular, the invention includes the composition of a novel fuel additive based on enriched bioethanol.

Improving the ecology by reducing the amount of harmful substances in fuel combustion products is a major problem of our time in the Baltic region. It is estimated that 70-85% of environmental pollution in major cities around the world is caused by the operation of automotive transport. Particulate matter resulting from incomplete combustion of motor fuels causes cancer in humans and animals. Therefore, reducing the amount of incineration products in the exhaust gas from motor fuels is an important environmental problem. Additives to the combustion can be solved by mixing them with the hydrocarbon fuel used. The most rational way would be to use fuel containing oxidant ethyl alcohol produced from renewable vegetable raw material, enriched with combustion catalysts, whose composition and quantities of combustion products comply with the requirements of the European Union.

In recent years, there has been a trend towards fuel formulations based on oxygen-containing organic compounds (hereinafter referred to as oxygenates), including aliphatic alcohols such as lower alcohols. Reference is made to U.S. Patent No. 4,282,2008 and many other U.S. patents, as well as WO 93/24593; WO 01/18155, RU 2068871, RU 2114898, EP

1196513, LT 3299 et al. When such additives contain ethanol, it is usually present in combination with significant amounts of other oxygenates.

Oxygenates-based additives have a positive effect on the combustion process of hydrocarbon fuels. However, known ethanol-containing analogues such as LT 3299, RU

2129141, the Ukrainian DPD Supplement (TS U 301.83376.001-2000) and others, have the common drawback of inadequate combustion speed and most importantly incomplete fuel combustion. Therefore, the use of ethanol-containing fuel additives without combustion catalysts consumes significantly higher amounts of additives to achieve a similar ecological effect.

Some fuel additives use metal compounds in the form of various complex compounds or metal salts with organic ligands. Examples include WO 00/11119 (Na, K, Mg, Ca or Sr salts), WO 87/01720 (organic and inorganic).

Cu, Fe, Mn salts in combination with different oximes and ethanolamines), etc. There is also a known fuel additive (WO 86/03492) containing 0.01 to 1.0 parts / min. parts of a fuel complex platinum group metal compound and from 0.25 to 5.0% by weight of a lower alcohol such as ethanol. The combination of two or more combustion catalysts - organometallic compounds in fuel additives is disclosed in patents and patent applications EP 0112219 (at least one lanthanide metal and at least one ferric metal organic acid salt), WO 97/40122 (two or more group I metal compounds). ): WO 98/04655 (combination of organometallic compounds of at least three metal groups wherein (M1) Fe, Mn, Co, Ni; (M2) - Ce, La, Nd, Pr; (M3) - Ba, Sr, Ca, Li); WO 99/21941 (Zn, Sr, Ca oxides, hydroxides or organic peroxides of several metals of Group IIA or IIB).

At least since 1957, literature (for example, H. Lamprey, Annals of the New York Academy of Science, 519, 1957, p. 22) mentions the possibility of using metal enolates, namely metal acetylacetonates, as combustion catalysts. However, this possibility has not yet been fully explored and exhausted, and is relevant and developing in recent years (patents RU 2027742, RU 2158289, RU 2159795, US 4474580, etc.).

A known (RU 2159794) composite fuel additive containing tetraethoxysilane and its hydrolysis products - dimers, trimers, tetramer impurities, and 0.1-1.0% by volume of any of Fe (III), Cr (III), Mn (III) or Co (III) acetylacetonates. The authors of the said patent estimate the use of such an additive to reduce carbon dioxide by 20-85%; non-combustible hydrocarbons -15-80%; nitrogen oxides content -15-55%; smoke - 40-90%; benzpyrene content - 15-70%. The authors do not specify with which engines the following significant reduction was obtained: Depending on engine life, an error can be unduly increased. In addition, tetraethoxysilane hydrolysis products can adversely affect the performance of the cylindrical piston portion of the vehicle.

The technical object of the present invention is to provide an efficient and economical fuel additive that provides improved eco-performance without generating degradation in performance and reducing fuel consumption. The use of ethanol as a renewable nutrient as a fuel additive would, in addition to addressing the ecological challenge, also ensure the exploitation of the potential resources and potential of ethanol production from sugar beet.

To solve the problem, a new fuel additive based on enriched bioethanol is proposed containing a mixture of iron (III) acetylacetonate and copper (II) organic compound with the following component ratio (w / w):

Mixture of iron (III) acetylacetonate and copper (II) organic compound 5 in the ratio 80-90: 10-20 0.001 - 0.50

Refined bioethanol remaining.

According to the present invention, a suitable copper (II) organic compound in the additive may be a novel copper (II) chelate synthesized by the inventors based on the product of condensation of acetoacetylferocene with ethylenediamine (hereinafter [Fe (acac)] 2enCu) according to structural formula I

C ₅ H ₅ FeC ₅ H ₄ COCH ₂ (CH ₃ ) C = NCH ₂ CH ₂ In) j = C (CH 3) CH ₂ COC ₅ H ₄ FeC ₅ H ₅ (I) '' Cu '

This copper (II) chelate is an orange-red solid crystalline with a melting point of 205-210 ° C, soluble in hydrocarbons (toluene). The compound was prepared in a manner known to those skilled in the art of complex chemistry.

Other copper (II) organic compounds are also suitable, such as:

- copper naphthenate, copper oleate, etc .;

organic salts of an inner copper complex in the form of alkylaminoalkylene ketone derivatives such as 1-methylaminobuten-1-one-3-o, 1-ethylaminobuten-1-one-3-o, 1-methylamino20 penten-1-one-3-o, 1 -methylamino-hexen-1-one-3-o, 1-methylamino-octen-1-one-3-o, 1-methylamino-5-methylhexen-1-η-3-ο, 1-ethylamino-5-methylhexen-1-η-3 -ο, 1-isopropylamino-5-methylhexen-1-one-3-o, 2-methylaminopenten-2-one-4-o and other copper derivatives;

- copper derivatives of salicylalimine, such as salicylalethylimine, salicyl isopropylimine, salicylalbutylimine, salicyl limexyl imine, salicyl alhexylimine, salicyl alheptylimine, etc .;

-25 - Copper (II) acetylacetonate.

The fuel additive of the present invention contains bioethanol enriched in the rectification process with the following oxygen-containing components: propyl, isopropyl, butyl, isobutyl, amyl, isoamyl alcohols, etc., produced in the production of ethyl alcohol from vegetable raw materials.

Unlike hydrolyzable ethyl alcohol, the bioethanol used in the present invention is obtained from a renewable feedstock by the rectification of a microbiologically derived alcohol broth containing lower temperature distilled aldehydes, ethers and esters, ketones, alcohols and other acetaldehyde. The listed substances (acetaldehyde) are intermediate ethanol biosynthetic intermediates obtained from alcohol-producing yeasts (Fungi class, Unicellomycetalis series comprising the Sacharomycetaceae, Schizosacharomycetaceae, Sacharomycodaceae families).

An additional positive effect is that the rectification process can be carried out in two columns without isolation of the ethers and aldehydes or the fuselage fraction. This, in addition to reducing the cost of bioethanol, makes it possible to narrow the technological scheme of ethanol production and rectification and, in some cases, to do without separation and subsequent blending of components, as is known in the art.

A significant part of Lithuanian agriculture is oriented towards sugar beet growing, therefore the republic has excess resources of sugar beet production from ethyl alcohol. The use of bioethanol in the proposed fuel additive predicts the consumption of all this surplus, which is quite an important factor in stabilizing the country's economy, which prevents farmers from over-profiling. Not only does the use of bioethanol enriched in this invention ensure high ecological requirements, but at the same time results in a significant reduction in both the fuel additive and the fuel composition as a whole.

The production of ethanol from the raw material (beet), alcoholic fermentation and rectification results in the formation of a certain amount of high-temperature distillate fraction. Studies have shown that the presence of small amounts of this fraction in the additive can further improve fuel performance by reducing their freezing point.

The enriched bioethanol of the present invention additionally has a denaturing additive, such as isopropyl alcohol and denatonium benzoate (bitrexate), or methyl ethyl ketone and methyl isobutyl ketone, or other, as designated by regulatory enactments of the Republic of Lithuania.

-25 In addition to the necessary components (iron acetylacetonate / organo-copper mixture and bioethanol), the fuel additive may contain at least 0.02% tetraethoxysilane, free from hydrolysis product impurities (at least 99% by weight of the basic substance). The alcoholic medium of the additive of the present invention does not undergo hydrolysis of tetraethoxysilane and not only its dimers and trimers, but also other siliceous gels and irritants capable of decomposition to

SiO ₂ , which can adversely affect the cylinder-piston part of the car

The invention and its industrial application are illustrated but not limited to the following examples and test results.

example. Addition Preparation:

To a mixture of 0.4 g of a mixture of copper and iron acetylacetonates taken at a ratio of 10:90, 1 liter of sugar beet bioethanol denaturing with isopropyl alcohol and dinatonium benzoate (bitrexate). Stir the mixture at room temperature until completely dissolved.

The resulting fuel additive is a single clear, slightly oily liquid with a characteristic odor. The additive is stable and effective both for immediate use and for longer periods of time; it blends well with all types of widely used motor fuels (including A92, A-95, A-98 petrol and others).

. Methods and results of tests for the generation of soot

The duration of the spark plug work until it became malfunctioning was determined in the 3HJ110 130 engine single cylinder section. The tests were performed according to a known methodology (RU

2019559) in separate 5 hours. duration cycles with the engine running in alternating modes. The formation of burns in the spark plug A11 of 0.65 mm was evaluated by the following criteria: reduction of spark gap; change in mass of spark plug, nature of scorch on spark plug electrodes. The change in spark gap was monitored with the projector using a 100x magnification; The nature of the scaling of the spark plug electrodes was evaluated using the MMH-8 optical microscope.

The octane number of the fuel composition with the additive of the present invention was in the same range as the fuel without the additive.

The analysis of the data presented in Table 1 shows that the scorch produced when the fuel containing the additive of the present invention is burned differs substantially and its accumulation on the spark plug electrodes occurs at different rates compared to the base composition without the additive. Burning of the basic hydrocarbon composition leaves homogeneous dense lacquer-like slags, and when burned in an engine fuel with the additive of the present invention, friable microporous slags are formed that are easily removed.

Table 1

For example a sequence number. Attachment: Component composition, ratio Test duration, hours Spark Plug Mass Increase, mg Spark plug spark gap, mkm Poison on nature of spark plug electrodes (magnification 50x) 2 Without attachment - - 640 Homogeneous dense 5 0 640 in the form of varnish 10th 2 640 dross 15th 3 640 20th 4 635 25th 5 635 30th 5 630 40 8th 625 50 10th 600 60 10th 600

continuation of the table

3 10%; 5 12th 610 Purios iron (III) 10th 22nd 530 microporous acetylacetonate and 15th 34 500 copper (II) 20th 46th 450 dross acetylacetonate 25th 55 400 mixture in ratio 30th 52 410 85:15 40 55 400 50 50 415 60 51 410 4 0.5%; - 640 Purios iron (III) acetylacetonate and 5 10th 3 7th 630 620 microporous copper (II) 15th 11th 590 dross acetylacetonate 20th 15th 580 mixture in ratio 25th 20th 570 85:15; 30th 24th 560 additionally possessing 40 31st 530 0.02% Si (OC ₂ H ₅ ) 4 50 31st 520 ratio Si: Fe (III) 5: 1 60 30th 510 7th 0.001%; - 640 Purios iron (III) acetylacetonate and 5 10th 0 2 640 640 microporous copper (II) 15th 2 640 dross acetylacetonate 20th 3 635 mixture in ratio 25th 3 635 85:15 30th 4 630 40 5 625 t 50 7th 600 60 7th 600 8th 0.01%; «. - 640 Purios iron (III) acetylacetonate and 5 10th 0 2 640 640 microporous of copper (II) chelating 15th 2 640 dross of the complex 20th 2 635 [Fe (acac)] 2enCu 25th 4 630 mixture in ratio 30th 5 625 85:15 40 7th 615 50 10th 600 60 9th 600

The nature of the burns using the additive of the invention, which contains an internal copper complex of an organic copper salt, a copper salicylalimine derivative, of an organic copper compound.

The use of the additive of the present invention as compared to the basic hydrocarbon composition is characterized by the formation of porous deposits which are easily removed from the surface of the spark plug by a stream of combustion products.

Concentrations of less than 0.001% of a mixture of iron acetylacetonate and organo-copper are difficult to detect by conventional chemical analysis methods. Adding larger amounts of the proposed additive (eg 10%) noticeably reduces the spark gap of the spark plug, although not yet stopping the engine. However, adding such large quantities is not economically justified.

The thermal stability studies of the copper (II) and iron (III) β-acetylacetonates in ethanol vapor conducted by the present inventors have shown an unexpected intense exothermic effect, melting that does not occur in an inert atmosphere or in the air. The effect is observed at temperatures of about 300 ° C for copper acetylacetonate (85% weight loss) and about 350 ° C for iron (III) acetylacetonate (12% weight loss). This suggests that the use of an organo-copper in combination with ferric acetylacetonate in the ratio set forth in the present invention not only enhances the catalytic activity but also results in a synergistic effect, particularly in the alcoholic medium.

Table 1 also shows that the results of other tests confirm that the use of enriched bioethanol with a mixture of organo-copper (II) and iron (III) -acetylacetonate has a positive effect on the formation of friable microporous deposits on the electrodes of the spark plug lacquer-like sediment. This eliminates the use of scaling agent and facilitates engine maintenance.

Methodology and results of ecological parameters research

Addition of 0.01% of the additive of the invention to A-92 grade gasoline resulted in comparative studies with the PEUGEOT-405GL 1998. shows a motor vehicle (engine capacity 1600 cm ³⁾ and the idle optimaliosios a construction load modes. The exhaust gas concentration was determined using a Gas Gas Analyzer REGA-7000 from Nicolet Instrument Corp., Madison, USA; the results are shown in Table 2.

table

For example a sequence number. Type of tests The composition of the exhaust gas HC, g / km CO, g / km NO _x , g / km co ₂ , g / km HC + NO _X , g / km 9th A-92 gasoline, idle 2.27 42.22 3.38 200.70 5.64 10th A-92 gasoline, optimum load 1.88 43.40 2.78 207.87 4.67 11th A-92 gasoline and 0.01% additive according to Example 1; idle 1.77 37.27 2.87 220.20 4.64 12th A-92 gasoline and 0.01% additive according to Example 1; optimum load 1.44 24.89 2.99 244.90 4.43 13th A-92 gasoline and 0.01% additive according to Example 4; optimum load 1.42 25.10 3.06 257.7 4.48

From Table 2, it can be concluded that the addition of the inventive additive to motor fuels results in a significant improvement in the quality of the exhaust gas, which ultimately contributes to the environmental performance of the environment.

In addition, the nearly 20% increase in CO ₂ emissions indirectly reflects the increase in engine power.

Claims (3)

DEFINITION OF INVENTION 1. An ethanol-based fuel additive having a combustion catalyst, characterized in that it contains enriched bioethanol and the combustion catalyst comprises a mixture of iron (III) acetylacetonate and copper (II) organic compound in a proportion by weight: Mixture of iron (III) acetylacetonate and copper (II) organic compound in a ratio of 80-90: 10-20 0.001-0.5 rest. 2. Fuel additive according to claim 1, characterized in that the copper (II) organic compound is copper naphthenate, a salt of an inner copper complex in the form of alkylaminoalkylene ketone derivatives, a copper salicylalimine derivative, a copper acetylacetonate or a copper chelate based on acetoacetylferocene condensation product. 3. Fuel additive according to claims 1-2, characterized in that it additionally contains at least 0.02% tetraethoxysilane free from hydrolysis impurities in the ratio of silicon: iron (III) from 1: 1 to 10: 1. 4. Fuel additive according to claims 1-3, characterized in that it contains bioethanol produced from a renewable nutrient such as sugar beet rectified by addition, which may additionally contain an ether and aldehyde fraction and / or a fuselage fraction and a denaturing additive. 5. Copper chelate based on the product of the condensation of acetoacetylferocene with ethylenediamine according to the structural formula