PL217137B1 - Universal bioester additive package - Google Patents

Description

Description of the invention

The subject of the invention is a universal package of additives for bioesters, especially fatty acid methyl esters, as an alternative fuel to diesel fuel.

It is known that fatty acid methyl esters (FAME) of plant and / or animal origin as so-called renewable fuels, due to the oxygen content in their chemical composition (fuel borne oxygen) have a positive effect on the combustion processes in self-ignition engines and thus reduce greenhouse gas emissions and toxic exhaust components such as carbon monoxide, unburned hydrocarbons, solid particles (PM2.5 and PM10) and NOx ("Impact of Biodiesel Emission Products from a Multi Cylinder Direct Injection Diesel Engine on Particulate Filter Performance" - SAE Paper No. 2009-01-1184) and ("Environmental Aspects of Biofuels in Road Transportation" - Environ. Chem. Lett. 2009, 7, 289-299).

From the descriptions and applications of US 525126, US 5532392, US 6440057, WO 99/26913, US 6489496, US 6818026, EP 1126011, US 7622600, US 7695533, US 2008/0015375, EP 1878716 and US 2008/0047194 it is known that the esters the alkyl fatty acids of vegetable oils are obtained by transesterification of the triglycerides contained in these oils with the use of alcohols, preferably methanol, and acidic or basic catalysts.

The method of producing fatty acid methyl esters (FAME) and purifying the crude product from glycerin, transesterification catalyst, methanol, monoacylglycerols (MAG), diacylglycerols (DAG) and triacylglycerols (TAG) and lipophilic impurities in the form of free non-acylated sterol glycosides (FStG), has fundamental influence on the functional properties of the obtained bioester.

The method of purifying bioesters from contaminants from the production process is known from US 2008/0092435, US 2009/0025277, US 2009/0223118 and US 2010/0212219.

It is known that the storage conditions of fatty acid methyl ester (FAME), such as storage temperature, air access, the presence of metallic impurities such as copper, nickel, iron - affect the oxidative stability of the bioester, expressed by the OIT (Oxidation induction time) or the oil stability index. OSI (Oil Stability Index) ("Effect of Temperature on the Oil Stability Index (OSI) of Biodiesel" Energy and Fuels, 2008, 22, 675-662). Shortening the oxidative induction period of bioester increases its viscosity, acid number, peroxide number and resins with strong adhesive properties.

The patent description PL 203138 describes a method of increasing the oxidative stability during storage of biofuel for a compression ignition engine by using 2,6-di-tert-butyl-p-cresol.

From the patent application WO 2007/145738 a mixture of oxidation inhibitors for biofuel intended for compression ignition engines is known, which is a mixture of diamines and phenols with a steric hindrance.

Moreover, it is known that storage and distribution conditions of bioesters increase the susceptibility of FAME to microbial contamination. This is manifested by precipitation and sludge, tendency to emulsify, and stable emulsions increase its susceptibility to hydrolysis, increase in acid number and corrosivity of the bioester ("Microorganisms in Diesel and in Biodiesel Fuels" - Technical paper - Acta. Chim. Slov. 2007. 54 , 744-748).

The result of microbial infection is turbidity and deterioration of bioester filterability, increase in impurities in the form of sediment and sludge, fuel color change, increase in viscosity and corrosive properties (Anaerobic Metabolism of Biodiesel and Its Impact on Metal Corrosion "- Energy Fuels, 2010, 24, 2924-2928 ).

The development of biofilm strongly adhering to the walls of the tanks favors the biocorrosion of steel, especially pitting corrosion, which is very difficult to monitor and causes damage to the walls of the tanks and the risk of bioester leakage.

Biocidal additives play an essential role in preventing and overcoming microbial problems in fuels and have been the subject of many patents.

Organic boron compounds preventing the growth of microorganisms in hydrocarbon fuels are known from patents US 3,523,014, US 3,873,279, US 3,877,890 and US 4,718,919.

PL 217 137 B1

Hexahydro-1,3,5-tris (2-hydroxyethyl) -S-thiazine is known as a biocidal additive for hydrocarbon fuels from US 4,585,462 and US 4,609,779.

The Polish patent specification PL 201210 describes an additive with biocidal activity for fuels, in which the biocidal agent is 5-chloro-2-methyl-4-isothiazolone-3 and / or 2-methyl-4-isothiazolone-3 and / or 2- octyl-4-isothiazolone-3 and / or 1,2-benzisothiazolone-3 stabilized with organic stabilizers.

The Polish patent description PL 207 780 also describes an additive with a biocidal and stabilizing effect, especially for fuels containing biocomponents. As a biocidal substance, the additive according to PL 207780 contains methylene bis (thiocyanate) and / or isothiazolones-3, such as 2-methylisothiazolone-3 and / or 2-ethylisothiazolone-3 and / or 2-propylisothiazolone-3 and / or 2- isopropylisothiazolone-3 and / or 2-butylisothiazolone-3 and / or 2-isobutylisothiazolone-3 and / or 2-tert-butylisothiazolone-3 and / or 2-hexylisothiazolone-3 and / or 2-octylisothiazolone-3 and / or 2-isothiazolectyl 3 and / or 3-decylisothiazolone-and / or 2-tridecylisothiazolone-3 and / or 2-octadecylisothiazolone-3 and / or 2-cyclopentylisothiazolone-3 and / or 2-phenylisothiazolone-3 and / or phenoxyethylisothiazolone-3 and / or 2- benzylisothiazolone-3 and / or 2- (thiocyanomethylthio) benzothiazole and oxidation inhibitors of the tert-butylated phenol and / or methylphenol type and / or dimethylphenol and / or isobutylphenol and / or methylene bis phenol and / or nonylphenol and / or octylphenol and / or methoxyphenol and / or hydroquinone.

It is known from the literature that the oxidative induction period (OIT) of a bioester depends on the percentage of unsaturated fatty acid methyl esters in FAME. It is known that palm oil methyl ester, POME (Palm Oil Methyl Ester), has the highest OIT value, expressed in hours, and the lowest soybean oil methyl ester, SOME (Soy Oil Methyl Ester). There is also a close relationship between the oxidative induction period (OIT) and the low temperature fluidity of FAME. ("Blending Effects of Biodiesel on Oxidation Stability and Low temperature Flow Properties", Bioresource Technology, 99, 2008, 1196-1203 and "Influence of Fatty Acid Composition of Raw Materials on Biodiesel Properties", Bioresource Technology 100, 2009, 261-268 ).

US Patent No. 6,015,440 discloses a method of producing a biofuel for a compression ignition engine with a reduced viscosity and a pour point below 32 ° F (0 ° C) by mixing FAME with 1,2,3-tritert-butoxy propane. In contrast, according to US Patent No. 6,174,501, the reduction of the pour point below 0 ° C is achieved by mixing the FAME with 1,2,3-tritert-butoxy propane or 1,2,3-tritert-pentoxy propane.

According to US Patent No. 6409778 and EP 1032620, in order to improve the low-temperature fluidity of the biofuel, it is recommended to use a terpolymer that contains 48% m / m to 98% m / m of a monomer which is an ester of (meth) acrylic acid and high molecular weight alcohols with a carbon content in the alkyl chain from 8 up to 30, 2% m / m up to 30% m / m monomer of (meth) acrylic acid ester and alkoxylated alcohols, where the amount of alkoxy groups is from 1 to 30 and 0% m / m to 30% m / m of monomer (meth) methyl, ethyl, propyl, butyl or styrene acrylate.

Also according to the patent application US 2006/0288637 to improve the low temperature fluidity and cloud point of the bioester obtained from palm oil it is recommended to use 0.1% m / m to 5.0% m / m polyalkyl methacrylate additive under the trade name Viscoplex 10-305.

The main goal of the invention is to obtain a universal package of additives intended for the refining of bioesters, especially fatty acid methyl esters as an alternative fuel to diesel oil and as a bio-component in a mixture with hydrocarbon fuels, effectively preventing microbial infection, as well as bioester oxidation processes under storage and transport conditions as well as pitting corrosion. pumps, tanks, transmission pipelines and fuel system systems, also showing improved low-temperature fluidity properties resulting from the synergistic effect that occurs when using low-temperature viscosity modifiers in the universal additive package.

It was surprisingly found that the universal package of additives for bioesters according to the present invention, especially fatty acid methyl esters, containing a biocidal substance, oxidation inhibitors, a corrosion inhibitor, a hydrocarbon solvent and a co-solvent, and possibly a metal deactivator, according to the present invention, preferably (in the autumn and in winter) low-temperature flow modifiers, facilitating the pumpability of bioesters and enabling the use of FAME as an independent fuel, thanks to the prevention of blockage of the cold filter at temperatures below -20 ° C.

The universal package of additives for bioesters, especially for fatty acid methyl esters, according to the invention contains a substance with a biocidal effect in the amount of 0.05% m / m to

PL 217 137 B1

25.0% m / m, preferably from 0.1% m / m to 20.0% m / m, where the biocidal substance is 2-thiocyanato-methylsulfenyl-1,3-benzothiazole, methylene-bis (thiocyanate) ), 2-n-octylisothiazolone-3, 1,2-benzisothiazolone-3, 2-N-butyl-1,2-benzisothiazolone-3 or their mixture, oxidation inhibitor in the amount from 0.5% m / m to 50.0% m / m, the oxidation inhibitors are alkylated monophenols and / or alkylated bis phenols and / or alkylated hydroquinones and 2,2,6,6-tetramethyl-piperidin-4-ol, corrosion inhibitor in the amount of 0.5% m / m to 10.0% m / m, hydrocarbon solvent in the amount of 10.0% m / m to 80% m / m and co-solvent in the amount of 2.0% m / m to 50.0% m / m and optionally : metal deactivator in the amount of 0.02% m / m to 5.0% m / m and bioester low-temperature fluidity modifiers in the amount of 2.0% m / m to 80.0% m / m.

As alkylated monophenols, the universal additive package contains 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl phenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2,6-ditert-butyl-4-isobutylphenol, 2,4,6-tritert-butylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,6- ditertbutylmethoxy-4-methylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,6-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-nonylphenol, 2,6- di-tert-4-octylphenol, 2,6-dinonyl-4-methylphenol, and preferably 2,6-di-tert-butylphenol.

However, as alkylated bis phenols it contains 2,2'-methylene-bis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (6-tert-butyl-4-ethylphenol), 2.2 ' -methylene-bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol, 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-methylene-bis (6-tert-butyl -2-methylphenol) and the alkylated hydroquinones are 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, preferably 2,6-di-tert-butyl hydroquinone.

As a corrosion inhibitor, the universal additive package contains nonylphenoxyacetic acid, dodecylphenoxyacetic acid, dodecenyl dicarboxylic acid, dodecyloxyacetic acid, N-oleylsarcosine or a mixture thereof, and preferably contains as a hydrocarbon solvent an aromatic petroleum fraction boiling up to 225 ° C and / or alkylbenzenes with a number of carbon atoms in the molecule at least 9 and straight chain or branched alkyls, while as a co-solvent it contains linear or branched aliphatic alcohols with the number of carbon atoms in the molecule from 4 to 15, preferably from 4 to 13 or ethers or polyethers or etheralcohols or esters of acetic acid and alcohols aliphatic with the number of carbon atoms in the molecule from 4 to 13; and esters of acetic acid and ethylene glycol and / or propylene glycol or esters of acetic acid and glycerin or 5,7-dioxundecane.

The universal additive package contains 1,2-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) propion-hydrazide or preferably N, N-disalicylidene-1,2-propanediamine as a metal deactivator, and a copolymer is included as bioester low temperature flowability modifiers ethylene vinyl acetate or ethylene vinyl propionate copolymer with a vinyl acetate or vinyl propionate content of 10.0% m / m to 40.0% m / m and an average molecular weight of 1,000 Daltons to 30,000 Daltons, preferably 2,000 Daltons to 10,000 Daltons, or phthalic anhydride diamide with primary amines such as n-dodecylamine or n-tridecylamine or hydrogenated fatty amines or hydrogenated tallowamine or esters of n-alkenyl succinic anhydride with hydrogenated fatty alcohols or primary amines such as n-dodecylamine or n-tridecylamine or n-tridecylamine , 2'-methylene bis (4-dodecylphenol) or alpha-dodecylphenoxy-omega-poly (propyleneoxy) propanol.

Compatibility of the universal additive package for bioesters, especially fatty acid methyl esters (FAME), as a standalone fuel for diesel engines as well as a biocomponent with hydrocarbon fuels in various amounts, both at low temperatures in winter (0 ° C to -25 ° C ), and at storage temperatures up to 60 ° C, is an additional positive feature that solves the problems of storage, transport and use of such fuel.

The invention is further explained in the following examples from 1 to 12 illustrating the composition of a universal additive package for bioesters, especially for fatty acid methyl esters, as a standalone alternative fuel for diesel fuel and as a bio-component with hydrocarbon fuels in mixtures marked as B-5, B- 7, B-10, B-20, the number after the letter "B" denotes the percentage of FAME in the fuel intended for use in diesel engines and the evaluation of selected performance properties of this universal additive package in test trials. These examples are not intended to limit the invention as they are illustrative only.

PL 217 137 B1

P r z k ł a d 1

1.1 g of 2-n-octylisothiazolone-3, 2.3 g of acetic acid ethylene glycol ester, 10.5 g of highly aromatic petroleum fraction with 99% aromatic hydrocarbon content were introduced into a mixer equipped with a circulation circuit and a temperature-regulating system. mass and boiling range from 182 ° C. to 225 ° C, 3.1 g of 2,6-di-tert-butylhydroquinone, 0.6 g of nonylphenoxyacetic acid. The included ingredients were mixed for 4 hours at a temperature of 25 ° C. to 35 ° C to dissolve the added solid oxidation inhibitor and obtain a homogeneous, clear liquid.

P r z k ł a d 2

0.8 g of N, N-disalicylidene-1,2-propanediamine, 3.8 g of ethoxylated butanol, i.e. an aliphatic alcohol with 4 carbon atoms and an average molecular weight of 118 Daltons, 20.2 g of an acetate copolymer, were introduced into the product of example 1. ethylene vinyl with a vinyl acetate content of 18% by mass, 27.6 g of phthalic anhydride diamide with n-dodecylamine and 30.0 g of alpha-dodecylphenoxy-omega-poly (propyleneoxy) propanol. The included ingredients were mixed for 2 hours at a temperature of 25 ° C. to 35 ° C to obtain a homogeneous, clear liquid.

P r z k ł a d 3

0.9 g of 2-thiocyanatomethylsulfenyl-1,3-benzothiazole, 12.1 g of 2,6-di-tert-butylphenol, 0.6 g of N-oleyl sarcosine, 1.2 g of acetic acid ester were introduced into a mixer equipped with a circulation circuit and a temperature-regulating system. and ethylene glycol and 21.6 g of highly aromatic petroleum fraction with a boiling range from 182 ° C. up to 225 ° C. The ingredients were mixed for 2 hours at the temperature from 30 ° C to 40 ° C until a homogeneous, clear liquid was obtained. Then 18.2 g of ethylene vinyl acetate copolymer with a vinyl acetate content of 18% (m / m), 31.4 g of 2,2'-methylene-bis (4-dodecylphenol), 11.0 g of alpha - dodecylphenoxy-omega-poly (propyleneoxy) propanol and 3.0 g of ethoxylated sec-butanol, i.e. an aliphatic ether alcohol with 4 carbon atoms and an average molecular weight of 118 Dalton. The included ingredients were mixed for 2 hours at a temperature of 30 ° C. up to 40 ° C to obtain a homogeneous, clear liquid.

P r z k ł a d 4

The product of example 1 was introduced in an amount of 600 mg / kg into bioester 1, which is fatty acid methyl esters (FAME) with the properties shown in Table 1.

P r z k ł a d 5

The product of example 2 was introduced in an amount of 2600 mg / kg into bioester 1, which is fatty acid methyl esters (FAME) with the properties shown in Table 1.

P r z k ł a d 6

The product of example 3 was introduced in an amount of 3300 mg / kg into bioester 2, a fatty acid methyl ester (FAME) with the properties shown in Table 1.

T a b l i c a 1

Marked feature Unit Bioester 1 Bioester 2 Cetane number - 53.3 52.3 Density at 15 ° C kg / m ³ 838.2 882.9 Sulfur content mg / kg less than 3.0 less than 3.0 Flash-point ° C 194 188 Coking residue in 10% distillation residue % (m / m) 0.1 0.1 Ash residue % (m / m) 0.001 0.002 Water content mg / kg 290 350 Kinematic viscosity at 40 ° C mm ² / s 3.88 4.43 Cold Filter Plugging Point (CFPP) ° C -12 -10

P r z k ł a d 7

Bioester 1 refined as in example 4 was tested for the biocidal effectiveness in a preventive test using the method according to ASTM E 1259, determining the content of microorganisms in the fuel phase using the IP 385 method. The applied methodology reflects a 4-fold refueling

The fuel in the distribution chain is brought into contact with a contaminated aqueous phase (called a vaccine) taken from fuel refinery tanks.

Table 2 presents the results of the obtained tests.

T a b l i c a 2

Time duration test (weeks) Product Material research The content of microorganisms in the fuel (com / l) and water (com / ml) phases bacteria oxygen yeast mushrooms mold 2 Bioester 1 from Table 1 fuel 3750 4200 4000 water 1.4x10 ⁸ 1.9x10 ⁴ 5.6x10 ³ Bioester 1 refined as in example 4 fuel Mon.40 Mon.40 Mon.40 water 5.5x10 ⁵ 1.0x 10 ⁴ 2.2x10 ² 8 Bioester 1 from Table 1 fuel 7200 8000 4500 water 3.0x10 ⁷ 9.4x10 ⁷ 4.0x10 ⁶ Bioester 1 refined as in example 4 fuel Mon.40 Mon.40 Mon.40 water 1800 1900 Mon 100

P r z k ł a d 8

Bioester 1 refined as in example 4 and bioester 2 refined as in example 6 were tested for oxidative stability according to PN-EN 14112. The test consists in passing an air stream through the tested sample at a temperature of 110 ° C. Volatile compounds released in the oxidation process are absorbed in demineralized water. The change in conductivity is recorded. The rapid increase of this parameter expressed in time units indicates the end of the oxidative induction period of the tested sample, which proves the fuel resistance to oxidation. The results are shown in Table 3.

T a b l i c a 3

Test fuel Test result: oxidative stability [h] 1 Bioester 1 from Table 1 8.49 2 Bioester 1 refined as in example 4 18.79 3 Bioester 2 from table 1 5.02 4 Bioester 2 refined as in example 6 8.13

P r z k ł a d 9

Bioester 1 refined as in example 4 and bioester 2 refined as in example 6 were subjected to an accelerated aging test according to ASTM D 4625 at the temperature of 43 ° C for a period of 3 months. The three-month storage period under test conditions corresponds to the one-year storage period at room temperature. Bioesters are biodegradable during storage. Determination of oxidized products (peroxide number) allows determining the stability of bioesters. Determination of peroxide numbers after the period of 1, 2 and 3 months from the beginning of storage of bioesters was carried out in accordance with the PN ISO 3960 standard. The results are shown in Table 4.

T a b l i c a 4

Test fuel Peroxide number according to PN ISO 3960 [mR O2 / kg] Storage period [months] 0 1 2 3 1 Bioester 1 from Table 1 2.3 85.3 148.5 310.0 2 Bioester 1 refined as in example 4 - 6.7 8.8 11.8 3 Bioester 2 from table 1 7.0 166.9 365.2 799.5 4 Bioester 2 refined as in example 6 - 9.2 15.9 38.5

PL 217 137 B1

P r z k ł a d 10

Cold filter blocking temperature (CFPP) tests were carried out according to PN-EN 116 standard for bioester 1 refined as in example 5 and bioester 2 refined as in example 6. The test consists in forcing through a standardized filter into a pipette under negative pressure and at reduced and controlled temperature at 1 ° C until the flow is blocked or slowed down, so that the filling time of the pipette exceeds 60 seconds or the test sample does not completely drain into the measuring vessel. Fatty acid methyl esters used as fuel for diesel engines should, in accordance with the EN 14214 standard, meet the requirements for fuels used in various climatic conditions. The results are presented in Table 5.

T a b l i c a 5

Test fuel Test result: CFPP [° C] 1 Bioester 1 from Table 1 -12 2 Bioester 1 refined as in example 5 -23 3 Bioester 2 from table 1 -10 4 Bioester 2 refined as in example 6 -twenty

P r x l a d 11

Bioester 1 refined as in example 5 and bioester 2 refined as in example 6 were tested according to the ASTM D 7501 standard. The test consists in storing the test sample for 16 hours at the temperature of 4.4 ° C, and then for 2.5 hours at temperature 20 - 22 ° C. After the specified time has elapsed, the sample is filtered through a set consisting of a filter with a diameter of mm and a pore diameter of 0.7 μm, under a pressure of 78.0 kPa. The time needed to filter 300 ml of the test sample is measured, which should be a maximum of 300 seconds. The results are presented in Table 6.

T a b l i c a 6

Test fuel Test result: Filtering time [s] 1 Bioester 1 from Table 1 558 2 Bioester 1 refined as in example 5 105 3 Bioester 2 from table 1 868 4 Bioester 2 refined as in example 6 201

P r z k ł a d 12

Bioester 1 refined as in example 5 and bioester 2 refined as in example 6 were tested for anticorrosive properties according to the ASTM D 665A standard. The test is based on the assessment of the corrosion degree of the steel pin placed for 6 hours at 40 ° C, in 300 cm ^{3 of} fuel and 30 cm ³ of distilled water mixed intensively. The mandrel corrosion grade is performed according to the NACE TM-02-75 scale, which has a range of A to E, with the A score being no corrosion. The test results for anti-corrosive properties are presented in Table 7.

T a b l i c a 7

Test fuel Test result: The degree of corrosion on the NACE scale 1 Bioester 1 from Table 1 D after 1 hour 2 Bioester 1 refined as in example 5 And after 6 hours 3 Bioester 2 from table 1 C after 1 h 4 Bioester 2 refined as in example 6 Apo 6 h

Claims (4)

Patent claims 1. A universal package of additives for bioesters, especially for fatty acid methyl esters, containing a biocidal substance, an oxidation inhibitor, a corrosion inhibitor, a hydrocarbon solvent and a co-solvent, characterized by the fact that it contains a biocidal substance in the amount of 0.05% m / m to 25.0% m / m, preferably from 0.1% m / m to 20.0% m / m, where the biocidal substance is 2-thiocyanatomethylsulfenyl-1,3-benzothiazole, methylene bis (thiocyanate) ), 2-n-octyl-isothiazolone-3, 1,2-benzisothiazolone-3, 2-N-butyl-1,2-benzisothiazolone-3, or their mixture, oxidation inhibitor in the amount of 0.5% m / m to 50.0% m / m, the oxidation inhibitors being alkylated monophenols, preferably 2,6-di-tert-butylphenol, and / or alkylated bis-phenols and / or alkylated hydroquinones, preferably 2,6-di-tert-butylhydroquinone, and 2,2 , 6,6-tetramethylpiperidin-4-ol, a corrosion inhibitor of 0.5% m / m to 10.0% m / m, such as nonylphenoxyacetic acid, dodecylphenoxyacetic acid, dodecenyl dicarboxylic acid, dodecyloxyacetic acid, N-oleyl sarcosine or their mixture, hydrocarbon solvent in an amount of 10.0% m / m to 80.0% m / m, the hydrocarbon solvent preferably being an aromatic petroleum fraction boiling up to 225 ° C and / or alkylbenzenes with the number of carbon atoms in the molecule at least 9 and straight-chain or branched alkyls, and a co-solvent in the amount of 2.0% (m / m) to 50.0% (m / m), which contains linear or linear aliphatic alcohols branched aliphatic with the number of carbon atoms in the molecule from 4 to 15, preferably from 4 to 13 or ethers or polyethers or ether alcohols or esters of acetic acid and aliphatic alcohols with the number of carbon atoms in the molecule from 4 to 13 and esters of acetic acid and ethylene glycol and / or propylene glycol or acetic acid glycerol esters or 5,7-dioxyundecane, and optionally: a metal deactivator in an amount of 0.02% w / w to 5.0% w / w, such as 1,2-bis- (3 , 5-di-tert-butyl-4-hydroxyphenyl-propio nyl) propion-hydrazide or preferably N, N-disalicylidene-1,2-propanediamine and bioester low-temperature flow modifiers in the amount of 2.0% m / m to 80.0% m / m, which are a copolymer of vinyl acetate and ethylene or Ethylene vinyl propionate copolymer with a vinyl acetate or vinyl propionate content of 10.0% m / m to 40.0% m / m and an average molecular weight of 1,000 Daltons to 30,000 Daltons, preferably 2,000 Daltons to 10,000 Daltons, or phthalic anhydride diamide with primary amines such as n-dodecylamine or n-tridecylamine or hydrogenated fatty amines or hydrogenated tallowamine or esters of n-alkenyl succinic anhydride with hydrogenated fatty alcohols or primary amines such as n-dodecylamine or n-tridecylamine or fatty amines or 2,2'-methylenebis ( 4-dodecylphenol) or alpha-dodecylphenoxy-omega-poly (propyleneoxy) propanol. 2. Universal package of bioester additives according to claim 2. The process of claim 1, characterized in that the alkylated monophenols are 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-ditert-butyl-4-isobutylphenol, 2,4,6-tritert-butylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2, 6-di-tert-butylmethoxy-4-methylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2,6-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-ditert-butyl- 4-nonyl-phenol, 2,6-di-tert-4-octylphenol, 2,6-dinonyl-4-methylphenol. 3. Universal package of bioester additives according to claim 2. A process according to claim 1, characterized in that the alkylated bis-phenols are 2,2'-methylene-bis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (6-tert-butyl-4-ethylphenol), 2 , 2'-methylene-bis (4-methyl-6-cyclohexyl-phenol), 2,2'-methylene-bis (4,6-diitert-butylphenol), 2,2'-ethylidene-bis (4,6- ditert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol, 4,4'-methylene-bis (2,6-ditert-butylphenol), 4,4'-methylene-bis (6-tert-butyl-2-methylphenol. 4. Universal package of bioester additives according to claim The process of claim 1, wherein the alkylated hydroquinones are 2-tert-butylhydroquinone, 2,5-di-tert-butyl hydroquinone.