CS275894B6 - Anti-wear additive for fuels over diesel or jet engines - Google Patents

Abstract

The invention relates to an anti-wear additive to fuels for diesel or jet engines improving their lubricity properties. The additive according to the invention contains a mixture of esters of mono- and/or polyfunctional alcohols and carboxylic acids. The number of carbon atoms in the alcohol part of the esters ranges from 2 to 18, and the number of carbon atoms in the acyl parts of the esters ranges from 3 to 45. The acyl parts of the esters may or may not contain double bonds in the carbon chain.

Description

1 CS 275894 B 6

BACKGROUND OF THE INVENTION The present invention relates to a fuel additive for diesel or jet engines which improves anti-wear properties.

On the basis of the latest knowledge, it can be stated that the demanding requirements of road and air transport on fuel cannot only be met through current or prospective oil processing technologies. From the point of view of the reliable operation of both the diesel and the jet engine fuel systems, it is essential that no solid phase, either in the form of n-alkanes, ice, or in the form of nutrients, which worsens fuel flow and wear, is removed from the fuel over a wide temperature range. components of the fuel system. It has been shown that by adding refining additives to diesel fuel jet engines, their utility properties can be effectively improved. Ingredients used in the production of kerosene and diesel fuel must be soluble in them, not even at extremely low temperatures, and washed out with water. Also, the long-term storage of fuel containing additives must not alter its chemical composition and efficiency.

Hydrotreated high refraction diesel and jet engines devoid of hetero-polar polar materials have poor lubricating properties, which are largely dependent on fuel system reliability. The results of long-term application tests of fuel jet engines have shown that one of the serious factors affecting the consumption of spherical surfaces of fuel pump plungers is the anti-wear and anti-impact properties of kerosene. The issue can be solved by adding fuel enhancing anti-wear properties. The lubricity-enhancing ingredients reinforce the lubricating film in such a way that they bind to the metal surfaces. They apply where there is a risk of transition from hydrodynamic lubrication mode to boundary mode, or to end of dry pregnancy. Presently, additives of this type are added to kerosene and diesel fuels produced at extremely low climatic conditions, or containing components obtained by hydrogenation cracking of oil distillates. Medium hydro-crack distillates are too "dry", their lack of lubricity may cause increased wear or seizure of diesel injection nozzles.

Diesel fuels are refined with additives that improve their low temperature, combustion and storage properties. The lubricity properties of "dry" diesel fuels obtained from medium distillates of the hydrogenation cracking product can be improved by the addition of 3 to 7% by weight. refined mineral oil, which, however, deteriorates the combustion properties of such diesel oil, especially in the direction of increasing the smoke fume of diesel engines. Typically, various water solubility enhancers based on ethylene glycol ethers are added to the aircraft petroleum oil to prevent ice formation in the fuel system, additives to prevent static build-up in fuel transfer, and antioxidants to improve thermal stability. The currently known and industrially applied anti-wear properties enhancing additives are predominantly based on fatty acid dimers either alone or containing residual amounts of catalyst used in their synthesis in the form of phosphoric acid esters. Also known are naphthenic acid additives derived from fractions with a distillation range in the range of 130 to 390 ° C found in petroleum with a special type composition. Said anti-wear additives provide sufficient lubricating properties to diesel and jet fuel, but naphthenic acids, for example, have the high density and kinematic viscosity at higher temperatures, and especially the safety precautions to be followed as their concentrated solution is strong corrosive. In addition, the raw material resources of production are limited. The disadvantage of using polar substances, for example on the basis of the acid-acid dimer, is that, when applied, the water separometric index of kerosene is lowered and their positive effect on lubricating properties is manifested only at higher concentrations (40 to 00 ppm by weight). .

The drawbacks of this kind are eliminated by the anti-wear (lubricant) additive for diesel fuel or jet fuel according to the invention, the main component of which is at least 85% by weight. the total additive is a mixture of single-functional and / or bifunctional and / or tri-functional and / or quaternary alcohols and carboxylic acids esters prepared synthetically and / or CS 275894 B6 2 obtained from plant precursors, wherein the number of carbon atoms in the alcohol portion is within the range of 2 to 18 and the number of carbon atoms in the acyl moieties of the esters is from 3 to 45. The carboxylic acids can be typical fatty acids derived from a variety of natural raw materials such as vegetable oils and animal oils. It can also be acids of petrochemical origin prepared, for example, on the basis of n-alkanes to C q, as well as the base of alpha-olefins obtained by polymerizing ethylene. Advantageous properties of the additive according to the invention are obtained when these carboxylic acids contain double bonds and the finished esters contain different kinds of acids from both the carbon-carbon chain and the number of double bonds in the chain.

Accordingly, the additives of the invention can be prepared synthetically by esterification of the abovementioned alcohols with carboxylic acids or can be obtained from natural, predominantly vegetable raw materials containing the chemical compounds of the invention. It is largely refined vegetable oils such as rapeseed oil, sunflower oil, peanut oil, loop corn oil. soybean oil and the like. The advantage of applying the anti-wear agent according to the invention is that it has no secondary unacceptable effects on the quality indicators of the fuel for diesel and jet engines. In addition, in diesel fuels it also increases the cetane number by 1 to 2 units and improves their low temperature properties. When applying the additive according to the invention, no corrosivity is observed. The recommended additive concentration of the present invention to improve the fuel density of diesel or jet engines is 0.0015 to 0.0040% by weight.

The following examples illustrate the advantages of an anti-wear additive according to the invention, but without limiting the scope of the invention in any way. EXAMPLE 1 Model blends of PL.l to PL.3 aviation kerosene were prepared on a laboratory scale and contained 0.003 .mu.L of anti-wear additive A according to the invention. In addition to the invention, the PL.l model mixture contained a lubricating additive based on refined rapeseed oil, which is a mixture of fatty acid esters of glycerol, and after the hydrolysis of the rapeseed oil, the resulting fatty acid mixture was found to be it contains 57.5% by weight of oleic acid, 19 ¾ by weight of linoleic acid and 9 ¾ by weight of linolenic acid and 0.5 ¾ by weight of erucic acid.

The PL.2 model blend contained the naphthenic acid additive 8 obtained from the leaching products of the hydrocarbon fraction with a distillation range from the range of 150 to 360 ° C found in the oil of the special type composition.

The PL.3 model mixture contained a linoleic dimer with a content of 0.01% by weight. phosphoric ester.

Mainly kerosene bases are listed in Table 1.

Lubricant properties of model blends of aviation kerosene PL.l to PL.3 were verified for 1 hour at 1500 rpm and constant loading of 150 N beads according to the IP 300 methodology on a 4-spoke PLINT 4GP instrument. heated. After performing the tests, the value of the abrasive stop diameter is determined for each model mixture that includes the wear rate. The experimental results measured are shown in Table 2 and are compared to the wear rate of the aircraft without additive (PL.4). On the basis of the results obtained, it can be concluded that the anti-abrasion properties of kerosene-containing additive A according to the invention are superior compared to aviation kerosene without additive or additive. commercial production additives, and thus the novelty and superiority of the additive according to the invention. On the basis of experimental results, it can be stated that the lubricant additive of the invention does not negatively affect the performance of the model aircraft kerosene mixture, whereas the anti-abrasive additive C has a negative effect on the separometric index value. It was shown that the spectroscopic index was reduced by 15 units at a concentration of 30 ppm by weight. of additive C 3 CS 275894 B 6 compared to aviation kerosene without additive, respectively. 11 units with respect to the additive of the invention. In view of the reliable operation of the nozzle engine fuel system, the parameter is also of great importance as it characterizes the ease of separating water from the fuel and operating the engine. Example 2

Lubricant properties of model mixtures of aviation kerosene PL.l to PL.4 prepared in the sense of Example 1 were verified according to the methodology set out in ČSN 656254. The main indicator of the result of the evaluation is the highest load at which the ball does not strike. The determined CCP values (ball machine number) are shown in Table 3 and are compared to critical load when returning PL.4 kerosene without additive. The results show that the fuel containing additive A according to the invention is characterized by improved anti-gypsum properties and thus its chemical composition has a beneficial effect in the direction of reduction of the amount of wear expressed by the CCP. Example 3

Esterification of pentaerythritol with a mixture of carboxylic acids having a carbon number of from 5 to 12 produced a synthetic anti-wearer D which was added to the kerosene at a concentration of 0.0025% by weight. (PL.5) and diesel fuel obtained by hydrocracking vacuum distillates at a concentration of 0.005 wt. (NM.2). Lubricant properties of model mixes PL.5 and NM.l to NM.2 were verified on a four-ball PLINT apparatus (4GP podium of the method described in Example 1. The results obtained are shown in Table 4 and compared to the average oder kerosene trace diameter values) without additive (PL.4), non-doped with diesel oil NM.l. Example 4 In laboratory scale, esterification of 1,6-hexanediol with a mixture of carboxylic acids having a number of carbons from 28 to 35, prepared from alpha-olefin with the addition of erucic acid at a concentration of 20% by weight This synthetically prepared pro-diode additive E was added to the base aircraft kerosene (PL.4) The model aircraft kerosene mix contained 0.002 wt%, 0.003 wt%, and 0.004 wt%, additive E .Conductive properties of the model mixtures were verified by the methodology of the ČSN 656254 methodology and on the four-ball instrument of the PLINT 4 GP type with the modified methodology IP 300 described in Example 1.

The measured results, which are presented in Table 5 and compared with the obtained values of the kerosene-free kerosene (PL.4), show that very good lubricity properties of the model aircraft-based kerosene are obtained when using the synthetically prepared epoxy additive E.

Table 1

Qualitatively indicators of kerosene without addition of additive improving properties

Quality Indicators Measured Value 'Density at 20 ° C, kg.m_ ^ 792 2 -1 Kinematic Viscosity, s, s - at 20 ° C 1.52 - at -40 ° C 6.09 CS 275894 B 6

Table 1- continued

Quality Indicators Measured Value Acidity, mgKOH / 100 cn? fuel 0,03 Iodine value in gj / 100 g fuel 0,07 Closed crucible temperature, ° C 47 Crystallization temperature, ° C -62 7 Thermal stability static, mg / 100 cm 0,81 Thermal stability dynamic according to methodology JFTOT - loss of pressure on the filter 0 - deposits on the preheater none Height of non-abrasive flame, mm 25,60 Luminometric number 58 Separometric index 99 Aromatic content,% wt. 14,300 Conductivity ', pSni- · * · 1.30

Table 2

Effect of addition of 0.003 wt. anti-wear additive A according to the invention, respectively. B and C in addition to the lubricating properties of kerosene and its other utility properties compared to base fuel without additive

Aviation kerosene outside the invention according to the invention PL.1 - PL.2 PL.3 PL.4 Additive type BC - A Abrasion trace diameter, ΠΙΠ1 0.834 0.896 0.916 0.813 Other utility properties Luminometric number 59 58 58 59 Separometric index 94 84 99 95 Thermal stability static, mg / 100 cm ^ samples 1,70 0,99 0,81 1,07 Thermal stability dynamic according to JFTOT - pressure loss 0 0 0 0 - deposits on preheater 0 0 0 0 Electrical conductivity pSm- '' '1.50 1.37 1.30 1.35 5 CS 275894 B 6

Table 3

Critical nanahing values for ball machine retention

Model blend Highest load, no sheath (N) The lowest load on the shank (N) PL.l 981 1,099 PL.2 893,991 PL.3 912 1,030 PL.4 873,981

Table 4

The values of the average oder traces measured according to the modified IP 300 methodology for the use of PL.4 and PL.5 aviation kerosene samples and the HM.l to NM.2 engine oil blends

Samples Oder value (mm) Kerosene without additive (PL.4) 0,916 Kerosene PL.5 0,805 NM.l 0,873 Diesel NM.2 0,754

Table 5

Influence of addition of anti-wear additive E on the lubricity properties of the aircraft

Additive concentration in kerosene (% by weight) 0 0.002 0.003 0.004 IP 300 methodology: - diameter of abrasive trace, mm 0.916 0.796 0.702 0.632

Claims (2)

CS 275894 B 6 6 Table 5 - continued Additive concentration in kerosene (% w / w) 0 0.002 0.003 0.004 According to ČSN 656254: - highest load, no damper yet, N - lowest load at which dump will occur, N 873 981 971 1 070 1 050 1 128 1 109 1 168 PATENT CLAIMS An anti-wear additive for diesel or jet fuel fuels, characterized in that its main component is at least 85% by weight. the total additive is a mixture of esters of monovalent and / or di-functional and / or tri-functional and / or quaternary alcohols and carboxylic acids, wherein the number of carbon atoms in the ester part is in the range of 2 to 18 and the number of carbon atoms in the acyl portions of the esters is from 3 to 45, and the corresponding components are the corresponding alcohols and carboxylic acids. 2. A fuel anti-wearer according to claim 1, wherein the carboxylic acids and acyl moieties of the esters are of the same or different types in terms of both the carbon chain length and the number of carbon double bonds. strings whose number has taken them to five.