CS269692B1 - Mixed additives for fuel oil and oil and fuel over diesel engines - Google Patents

Abstract

The solution relates to a mixed additive for heating oils and oils and fuel for diesel engines improving their low-temperature properties. The mixed additive contains a copolymer of ethylene and vinyl acetate with a vinyl acetate content of 17 to 55% by weight, low-molecular polyethylene formed as a by-product in the production of low- and high-density polyethylene by the high-pressure method, and a hydrocarbon solvent, which is formed by low-solidifying hydrocarbon fractions obtained in the processing of non-paraffinic and semi-paraffinic crude oil or in the solvent dewaxing of petroleum distillates or alkylbenzenes and higher-boiling products from side reactions in the production of alkylbenzenes.

Description

CS: 269-692 B1

BACKGROUND OF THE INVENTION The present invention relates to a mixed additive to, for example, fuel and oil and fuel, refueling engines, which improve their low temperature properties. At the present time, the low temperature requirements of fuel properties are being improved by diesel engines, which are often referred to as diesel, characterized by the most cloud point, freezing point and filterability limit. In diesel fuel that I don't contain! low-temperature fuel / depressant / low-additive additives, crystals of n-alkanes in a relatively large thin platelet form at low temperatures tend to combine into larger aggregates. If a depressant is present, n-alkenes are added to the surface of the crystals formed, and subsequent growth of the crystal is only possible at the corners. The modified crystals of the excluded n-alkanes are fine and therefore the pumpability of the fuel is improved. The mechanism of action of depressants in diesel fuel at lower temperatures is not yet fully understood. According to the catastrophic theory of crystallization of n-alkanes at low temperatures, the interaction of depressant molecules and n-alkanes occurs only after formation of the paraffin crystalline phase. It is believed, on the basis of a more recent theory, that the iteration of the n-alkanes and the excluded n-alkanes is mutual prior to the exclusion of higher n-alkanes. In the petroleum fractions, the n-alkanes present form non-molecular structures which can be separated by higher temperatures than the crystallization temperature of the individual n-alkanes.

Depressant molecules attack the molecules of n-alkanes at the stage of formation of supramolecular structures and form complexes with them, hence the added diesel fuel additive βδβ is used to aggregate n-alkanes at temperatures above their crystallization. The effect of the added depressant depends largely on the chemical structure of the additive itself, the method of its preparation, the nature and composition of the components used in the production of the engine oil.

The low temperature depressant additives of the motor oil are specifically polymers with a characteristic molecular weight. They are used in doze to 650 ppm, but in most cases just add! and less to achieve the desired low temperature fuel properties for diesel engines.

Depressants based on copolymers of alpha-olefins and ethylene, ethylene and vinyl acetate, ethylene and alkyl methacrylates, respectively, are added to the motor fuels. chlorinated carbon-thanks. The best-known representatives are ethylene-vinyl acetate copolymer (EVA-copolymer) with a vinyl acetate content of from 17 to 53% by weight, respectively. ethylene and alkyl methacrylate / EMA-copolymer / β relative molecular weight of 1,000 to 2,500 units.

Authors Csl. AO 216286 proposed the application of low molecular weight polyethylene obtained in the production of low density polyethylene by a high pressure process which is suitable to reduce the freezing point of motor oil from paraffinic oils, but has no significant effect on the fuel filterability. This can be explained by the fact that low-molecular-weight polyethylene can contain even higher molecular weight moieties, resulting in its poor solubility and loss of depressant efficacy to reduce filterability. This deficiency is eliminated by treating low molecular weight polyethylene in the sense of Cs1. AO 253442 separates the relatively soluble higher portions thereof from the hydrocarbons by settling or filtration. However, more preferred is the centrifugation using a hydrocarbon solvent. The depressant thus prepared with a relative molecular weight of 1500 to 3000 units makes it possible to reduce the low temperature properties of motor oil, fuel oil and oil more efficiently.

SUMMARY OF THE INVENTION The present invention is concerned with the application of a mixed additive to both diesel fuel and diesel fuel oil, which significantly reduces their low temperature properties compared to the previously mentioned depressants. CS 269 692 B1

The modified additive of the invention contains from 3 to 35 wt. % ethylene-vinyl acetate copolymer and a vinyl acetate content of from 17 to 55% by weight, from 2 to 35% by weight; low molecular weight polyethylene formed as a byproduct in the production of low density polyethylene by a high pressure process from which insoluble heavier particles are deposited in the hydrocarbons by settling, filtering or centrifuging and from 30 to 95% by weight of a hydrocarbon solvent formed by low-fat hydrocarbon fractions obtained in the treatment of non-paraffinic or semi-paraffinic petroleum and / or in the disintegration of petroleum distillates and / or alkylbenzenes and / or retarding products from side reactions in the production of alkylbenzenes from which residues of the alkylation catalyst and high molecular weight coke forming fluxes have been removed and / or distilled from the fractions, wherein the alkyl benzene group contains from 3 to 52 carbon atoms. The presence of the mixed additive according to the invention is manifested by the fact that the growth of crystals of n-alkanes cured at lower temperatures is affected. The presence of the two components in diesel fuel results in the polyethylene forming the nuclei of the crystallization of the n-alkanes, and the EVA copolymer modifies the surface of the cured n-alkanes. The application of the mixed additive according to the invention results in a limited number of crystals resulting in a significant reduction in the freezing temperature and filterability of the motor fuels. It has been experimentally golden that the mixed additive has a potency compared to the use of the copolymers themselves, and thus synergism occurs when such a mixed additive according to the invention is applied. It has been found that the highest synergistic effect is obtained when the mixed additive comprises drawing portions of low molecular weight polyethylene soluble in alkylbenzenes or by raising the products of the reaction! in the production of alkylbenzenes and ethylene-vinyl acetate copolymers with a vinyl acetate content of from 35 to 40% by weight. in a mutual weight ratio of from 3.5: 1 to 12.5: 1, preferably from 4.8: 1 to 10.6: 1.

I document the following examples! the advantages and synergistic effect of applying the mixed additive according to the invention, without, however, limiting the subject matter of the invention in any way. Example 1 A low molecular weight polyethylene with a relative molecular weight of 4200 units was obtained as a byproduct in the production of polyethylene by a high pressure process. Low-molecular-weight polyethylene, after dissolution in the hydrocarbon solvent, formation of alkylbenzenes and by boiling products resulting in the production of cumene, from which the customs of the alkylation catalyst and high molecular weight coke formers were removed, in the form of a 10% solution / solution 1 / blasted in laboratory conditions the ALPA LAVAL LAPX 202 centrifuge at 9000 rpm for 20 minutes. Centrifugation at room temperature removed the less soluble constituents in the hydrocarbon solvent, which were combined in the resulting bottom layer containing 19.9% by weight. low-molecular weight polyethylene.Top clear layer containing 80.1 wt. 10-3 units of low molecular weight polyethylene / Component 1 / e and used in the preparation of the mixed additive according to the invention.

Copolymer of ethylene and vinyl acetate containing 38.7 wt. vinylacetate (Component 2) was dissolved in Component 1 at 40 ° C so that the relative mass of CS 269 692 B1 Component 1 and Component 2 was 9: 1. The prepared mixed additive 1 was used as an additive in the winter-type diesel fuel to reduce its low temperature properties. The freezing temperature and filterability of said low-temperature diesel fuel at the dew concentration of the additive 1 were compared. and Components 1 to 2 (except for the invention) shown in Table 1. The measured results show that when the mixed additive is applied, a synergistic effect is obtained in determining the freezing temperature and filterability of the winter type diesel fuel. I.e. That at lower yields Component 2 in the mixed additive 1, it is possible to achieve a better non-temperature property of diesel fuel when using the additives Component 1 and Example 2. Example 2 Low molecular weight polyethylene with a regulatory molecular weight of 4400 units soluble in a hydrocarbon solvent formed low-solidifying hydrocarbon fractions obtained from solvent dewaxing of petroleum distillates, 5% by weight of the solids were separated by settling. Lahsia, in the hydrocarbon solvent, the solubles (additive 4) were used as an additive to reduce the freezing temperature and filterability of the transitional type diesel.

Copolymer of ethylene and vinyl acetate containing 40.6 wt. vinylacetate / additive 3 / was added to the additive 4 at a temperature of 35 ° C so that the additive 3 to additive 4 was 1: 5 in the additive 2 additive. From Diesel Oil and Additive Additives 3 to 4 and Mixture Additive 2, respectively, were prepared to provide sample samples for which temperature and filterability were determined. The measured results shown in Table 2 show that the application of the mixed additive 2 (according to the invention) results in lower values for low temperature properties of the model samples of the motor fuel compared to the application of the additives of the invention (Additives 3 and 4). EXAMPLE 3 A low molecular weight 4320 unit low molecular weight polyethylene prepared as described in Example 1 was dissolved in a hydrocarbon solvent consisting of low-solidifying hydrocarbon fractions and a fraction of 183-335 ° C obtained by processing non-paraffinic and semi-paraffinic. , in the form of a 10% solution / solution A /. Heavy portions of low molecular weight polyethylene were collected on activated carbon by pressure filtration and the filtrate obtained contained 83.2% by weight. of the low molecular weight polyethylene was used as component (B) in the preparation of the mixed additive (3) by blending copolymer ethylene and vinyl acetate containing 39.4 wt. and a solution B in a weight ratio of 1: 5 to form a mixed additive 3. From the diesel fuel for the summer season and the mixed additive 3 (according to the invention) and additive 5 (except for the invention) model diesel blends were prepared so that a small resulting EVA-copolymer concentration (100, 200 and 300 ppm). In these model mixtures, the cloud point, freezing point and filterability limit were determined. Based on the experimental results achieved (Table 3), the application of the mixed additive 3 results in low-temperature low-temperature diesel fuel compared to the use of additive 5 alone. EN 269 692 B1 Example 4

The mixed additive 3 prepared in Example 3 was added to the diesel fuel for heating to give a small EVA-copolymers final concentration of 100, 200 and 300 ppm. For the prepared samples, a freezing point was determined. The experimentally obtained data shown in Table 4 are compared with the freezing point of the motor engine fuel without the additive improving its low temperature properties. Example 5 From the winter heating oil and the mixed additive 2 according to the invention, they prepared a model mixture of fuel oil to contain 1000, 2000 and 3000ppm of the mixed additive 2. In modeling aids and determined the cloud point and freezing temperature. The measured results are shown in Table 5 and are compared with the low temperature properties of the oil without depressant.

Table 1 Low Temperature Properties of Winter Type Diesel at Various Concentrations of Additive 1 (According to the Invention) and Additives Component 1 and 2 (Excluding the Invention)

Depressant type and its appearance ppm Low temperature properties in ° C Freezing temperature Filtration Mixed additive 1 / according to the invention / no additive - 18 - 9 1000 - 30 - 15 2000 - 37 - 18 3000 - 41 - 20 4000 - 43 - 21 KomDonent 1 / outside the invention / without additive - 18 - 9 3000 - 24 - 11 4000 - 28 - 12 6000 - 30 - 13 8000 - 31 - 14 Comoonent 2 (except of the invention / no additive - 18 - 9 200 - 29 - 14 400 - 33 - 18 600. - 36 - 20 800 - Π - 21

Table 2

Influence of the addition of the mixed additive 2 (according to the invention) and additives of additives 3 and 4 (except for the invention) on the low temperature properties of the transitional type CS 269 692 B1,

TemperatureCapacity ° C Filterability ° C Additive 4 (Excluding the Invention / Without Additive - 17 - 7 1000 ppm - 21 - 9 3000 ppm - 25 - 10 5000 ppm - 27 - 12 10000 ppm - 28 - 13 Additive 3 (Except Invention) 100 ppm - 24 - 10 200 ppm - 28 - 13 300 ppm - 30 - 15 500 ppm - 31 - 16 Mixed additive 2 / according to the invention / 600 ppm - 27 - 12 1200 ppm - 32 - 16 1800 ppm - 35 - 18 2400 ppm - 37 - 19 3000 ppm - 38 - 20

Table 3

Influence of addition (ppm by weight) of the meat additive 3 according to the invention and additive 5 (of the invention) at the same concentration of EVA copolymer, e.g. Solution B (except the invention) for low temperature summer type diesel

Temperatures ° C Pilotability ° C Turbidity Temperature ° C Solution B (Excluding Invention / Without Additive - 12 - 2 - 3 500 - 14 - 6 - 3 1000 - 15 - 7 - 4 1500 - 15 - 8 - 3 Additive 5 / of the invention / without additive - 12 - 2 - 3 100 - 18 - 8 - 3 200 - 22 - 11 - 3 300 - 24 - 13 - 4 Mixing additive 3 / of the invention / no additive - 12 - 2 - 3 600 - 20 - 11 - 4 1200 - 25 - 15 - 4 1800 - 28 - 17 - 3

Claims (2)

CS 269 692 B1 Table 4 Effect of Addition of Mixed Additive 3 on the Freezing Temperature of Diesel Fuel over Smoke e Concentration of BVA-Copolymer in Mixed-Weight 3 pp «Temperatures ° C without Additive - 6 100 - 13 200 - 17 300 - 19 Table 5 Effect of Addition mixed additive 2 for low temperature properties of fuel oil Addition of mixed additive 2 Temperature Temperature ppm turbidity ° C solidification ° C without additive ♦ 23 + 19 1000 ♦ 23 + 3. 2000 + 23 - 7 3000 + 23 - 11 PRBDMET V ΪΝ A LE Z U Mixing additive for heating oil and diesel engines for diesel engines improving their low temperature properties, characterized in that it contains from 3 to 35 wt. % of ethylene-vinyl acetate co-polymer having a vinyl acetate content of from 17 to 55% by weight; low molecular weight polyethylene formed as a byproduct of low density polyethylene by a high pressure process from which the insoluble heavy extracts were removed by settling by filtration or centrifugation and from 30 to 95 wt. hydrocarbon solvent consisting of low-carbon hydrocarbon fractions from 100 to 370 ° C obtained for the treatment of non-paraffinic or semi-paraffinic petroleum and / or hydrocarbon fractions obtained by dewaxing petroleum distillates with boiling point up to 489 ° C and / or alkylbenzenes and / or it feeds from the byproducts of the side reactions in the production of alkylbenzenes from which the residues of the alkylating catalyst and the high molecular weight coke-forming substances have been removed and / or fractions obtained therefrom, the alkyl group of the alkylbenzenes containing from 3 to 52 carbon atoms.