PL218043B1 - Multi-functional package of biocide and stabilizing additives - Google Patents

Description

Description of the invention

The subject of the invention is a multifunctional package of biocidal-stabilizing additives, especially for biofuels, and in particular for fatty acid methyl esters as a self-contained fuel, alternative 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 the emission of toxic exhaust components such as carbon monoxide, unburned hydrocarbons, particulate matter (PM) and NOx ("Impact of Biodiesel Emission Products from a Mutli-Cylinder Direct Injection Diesel Engine on Particulate Filter Performance" SAE Paper No. 2009-01-1184 ).

From the descriptions of patents and patent applications US 525126, US 6440057, WO 99/26913, US 6489496, US 6818026, EP 1126011, US 7622600, US 7695533, US 2008/0047194, US 2008/0015375 and EP 1878716 it is known that the alkyl esters of acids Vegetable fatty oils, used as biofuel, are obtained by transesterification of the triglycerides contained in these oils with methanol or ethanol.

The method of producing fatty acid methyl esters (FAME) and purifying the raw product has a great influence on the properties of the obtained biofuel.

Moreover, it is known that the storage and distribution conditions of the biofuel thus obtained increase its susceptibility to microbial contamination ("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 fuel filterability, increase of impurities in the form of sediment and sludge, fuel color change, increase of viscosity and corrosive properties.

For the development of the majority of microorganisms, the water phase is necessary for their development. Infection of fuel with microorganisms can occur in many ways. In many cases, microorganisms settle on the walls and dead spaces of the tanks where they come into contact with the condensation water.

Additives with biocidal activity play an essential role in preventing and overcoming microbial problems in fuels. Properly selected and applied at the dosage level depending on their biocidal activity, they allow to eliminate and control the growth of microorganisms.

Biocidal additives for hydrocarbon fuels have been the subject of many patents.

From GB 994,919, inorganic and organic silver salts solubilized with primary, secondary and tertiary amines, alkylphosphines and arylphosphines or substituted thiourea derivatives are known as biocides.

GB 1,307,097 for hydrocarbon fuels recommends the use of the alkylammonium salt of 2-mercaptopyridine oxide as a biocide.

According to patents GB 2151658 and EP 0147222, tert-butyl hydroperoxide or cumene hydroperoxide in a mixture with alkylphenols, alkoxyphenols, alkylarylphenols and a solvent is used as a biocide for microbiological protection of fuel products (aviation fuel), while for the microbiological protection of fuel for sea transport, it contains a biocidal composition additionally benzimidazole derivatives such as methyl-2-benzimidazole carbamate or butylcarbamoyl-2-benzimidazole carbamate.

Another group of additives with biocidal activity used in hydrocarbon fuels are organic boron compounds. According to US Pat. No. 3,523,014, a borated monoalkylhydroquinone is used as a biocide for the microbiological protection of gasoline.

In contrast, according to US patent 3,873,279, 1-hydroxy-3H-1,2-benzo-oxoborol is claimed as an anti-microbial agent in aviation fuel, and according to US patent 3,877,890 a mixture of 4-hydroxymethyl-2-phenyl is claimed as a biocide for aviation fuel. -2-boro-1,3-dioxocyclopentane and 5-hydroxy-2-phenyl-2-bororo-1,3-dioxocyclohexane.

Also according to US patent 4,718,919 and US 2004/0060229, a composition of organic boron compounds with biocidal properties for fuels claims 2-methoxy-ethanol and a mixture of 2,2'-oxybis (4,4,6-trimethyl-1, 3,2-dioxoborinan) and 2,2 '- (1-methyltrimethylenedioxy) bis (4-methyl-1,3,2-dioxyborinane).

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

According to EP 166 611, the active substance of the biocidal fuel additive is 5-chloro-2-methyl-4-isothiazolone-3 and 2-methyl-4-isothiazolone-3 mixed in a ratio of 3: 1.

EP 0315464 in turn discloses the use of orthoesters to stabilize isothiazolone in biocidal fuel additive compositions.

The Polish patent specification PL 201 210 also describes an additive with a biocidal effect 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. The additive according to PL 207 780 contains as biocidal substance 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-tertbutylisothiazolone-3 and / or 2-hexylisothiazolone-3 and / or 2-octylisothiazolone-3 and / or 2-isothiazertolone -3 and / or decylisothiazolone-3 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.

Biocidal additives for hydrocarbon fuels such as organic boron compounds, hexahydro-1,3,5-tris (2-hydroxetyl) -S-triazines, isothiazolones show good biocidal and biostatic properties, preventing microbiological contamination of these fuels, the development of organic biofilm and biocorrosion, but their use in FAME at concentrations recommended for hydrocarbon fuels is ineffective. It turns out that, despite the use of oxidation inhibitors, as in the case of fuels containing biofuels, the tendency to oxidize such protected biofuels is accelerated, which reduces their storage time.

The literature knows the influence of temperature on the oxidative stability of FAME, expressed by the oxidative induction period OIT (Oxidation Induction Time) or the Oil Stability Index (OSI) ("Effect of Temperature on the Oil Stability Index (OSI) of Biodiesel" Energy and Fuels , 2008, 22, 657-662).

Shortening the oxidative induction period of biofuel causes an increase in its viscosity, acid number and an increase in peroxides, which, as a result of interaction with biocides, cause their accelerated chemical decomposition and reduce their microbiological effectiveness. It manifests itself in the precipitation of sediments and sludge and favors the development of a biofilm firmly adhering to the walls of the reservoir, favoring steel biocorrosion (pitting corrosion).

The main objective of the invention is to obtain a multifunctional biocide-stabilizing additive package, especially for biofuels, the biocide of which is methylene bis (thiocyanate) and / or selected 3-alkylisothiazolones and / or 2-thiocyanato-methylsulfenyl-1,3-benzothiazole, effectively protecting the biofuel against microbial infection and selected oxidation inhibitors to prevent fuel oxidation under conditions of storage and transport.

An additional goal is to obtain such a multifunctional biocidal-stabilizing additive package for biofuels that would be compatible with the corrosion inhibitors required to protect storage tanks, pipelines, valves and also with the construction materials of a diesel engine, as this fuel is intended as an intrinsic fuel (B100). for diesel engines and can be used as a biocomponent with hydrocarbon fuels in various amounts, marked as (B-5, B-7, B-10, B-20).

Compatibility of the multifunctional biocidal-stabilizing additive for self-contained biofuels and fuels containing biocomponents with other additives used in modern engine oils is an additional positive feature of the invention, solving the operational problems of cars equipped with diesel engines.

It has surprisingly been found that such properties are possessed by the multifunctional package of biocidal-stabilizing additives for upgrading biofuels according to the present invention

A biocidal substance, oxidation inhibitors, an organic stabilizer, a corrosion inhibitor, a hydrocarbon solvent and a co-solvent, and preferably a metal deactivator.

The multifunctional package of additives with a biocidal and stabilizing effect, especially for biofuels, according to the invention contains the substance having a biocidal effect in the amount of 0.05% (m / m) to 25.0% (m / m), preferably 0.1% (m / m) / m) up to 20.0% (m / m), hydrocarbon solvent in the amount of 1.0% (m / m) to 90.0% (m / m), co-solvent in the amount of 1.0% (m / m) m) up to 50.0% (m / m), an oxidation inhibitor in the amount of 0.5% (m / m) to 60.0% (m / m) and possibly a corrosion inhibitor in the amount of 0.5% (m / m) / m) to 10.0% (m / m) and optionally an organic stabilizer in the amount of 0.05% (m / m) to 1.0% (m / m) and a metal deactivator in an amount of 0.03% ( m / m) to 5.0% (m / m), where the biocidal substance is methylene bis (thiocyanate) or 2-alkylisothiazolony-3 or 2-thiocyanato-methylsulfenyl-1,3-benzothiazole or their mixture.

The multifunctional additive package with a biocidal-stabilizing effect according to the invention contains 2-alkylisothiazolones-3, such as 2-n-octylisothiazolone-3 or 2-n-decylisothiazolone-3 or 2-n-undecylisothiazolone-3 or 2- (2,5, 3-5-trimethyl) hexylisothiazolone-3 or 2- (3,5,5-trimethyl) hexylisothiazolone-3 or 2- (2-methyl) octylisothiazolone-3 or 2- (5,7-dimethyl) octylisothiazolone-3 or 2- ( 3-8-methyl) nonylisothiazolone-3 or 2- (3,5,7-trimethyl) heptylisothiazolone-3 or 2- (2,8-dimethyl) nonyl-isothiazolone-3 or a mixture thereof.

As a hydrocarbon solvent, the package preferably comprises an aromatic petroleum fraction with a boiling point of up to 220 ° C and / or alkylbenzenes with at least 9 carbon atoms in the molecule and straight and / or branched alkyls, and the co-solvent is branched and / or linear aliphatic alcohols the number of carbon atoms in the molecule from 4 to 15, preferably from 4 to 13, or ethers or polyethers or ether alcohols derivatives of monohydroxy or polyhydroxy compounds or alkylphenol ethers or polyethers with the number of carbon atoms in the alkyl substituent from 4 to 15 or esters of straight and straight aliphatic alcohols / or branched hydrocarbon chain with the number of carbon atoms in the molecule from 3 to 15, preferably from 4 to 13, or esters of ethylene or propylene glycol or ethoxylated or propoxylated aliphatic alcohols with the number of carbon atoms in the alkyl molecule from 4 to 8 and organic monocarboxylic acids, or dicarboxylic acid or 5,7-dioxaundecane, and stabi the organic lyser is preferably 1,6-hexanediol nitrate or nitrite

1,6-hexanediol.

The multifunctional package of biocidal-stabilizing additives according to the invention contains as oxidation inhibitors 2-tert-butylphenol or 4-tert-butylphenol or 2,6-ditert-butylphenol or 2,4-di-tert-butylphenol or 2-tert-butyl-4,6- dimethylphenol or 2,6-di-tert-butyl-4-ethylphenol or 2,6-di-tert-butyl-4-n-butylphenol or

2,6-di-tert-butyl-4-isobutylphenol or 2,4,6-tritert-butylphenol or 2,6-di-tert-butyl-4-methoxyphenol or

2,6-di-tert-butylmethoxy-4-methylphenol or 2,6-dicyclopentyl-4-methylphenol or 2,6-octadecyl-4-methylphenol or 2,4,6-tricyclohexylphenol or 2,6-di-tert-butyl-4- nonylphenol or 2,6-di-tert-butyl-4-octylphenol or 2,6-dinonyl-4-methylphenol or 2,6-diphenyl-4-octadecyloxyphenol or 2,5-di-tert-butyl-4-hydroxyanisole or 3,5- di-tert-butyl-4-hydroxyanisole or 3,5-di-tert-butyl-4-hydroxyphenyl stearate, or preferably 2,6-di-tert-butyl-4-methylphenol, or 2-tert-butylhydroquinone or 2,5-di-tert-butylhydroquinone Or preferably 2,6-di-tert-butylhydroquinone, or 2,5-diitert-amylhydroquinone, or bis (3,5-diitert-butyl-4-hydroxyphenyl) adipate or 2,2'-methylene bis (6-tert-butyl) 4-methylphenol) or 2,2'-methylene bis (6-tert-butyl-4-ethylphenol) or 2,2'-methylene bis (4-methyl-6-cyclohexylphenol) or 2,2'-methylene bis (4,6-di-tert-butylphenol) or 2,2'-ethylidene-bis (4,6-ditert-butylphenol) or 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol) or 4 , 4'-methylene-bis (2,6-di-tert-butylphenol) lu b 4,4'-methylene bis (6-tert-butyl-2-methylphenol) or octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and contains N, N-dihydrazides as a metal deactivator , preferably 1,2-bis (3,5-diitert-butyl-4-hydroxyphenylpropionyl) propionhydrazide, or N, N-disalicylidene-1,2-alkylene diamine, preferably N, N-disalicylidene-1,2-propanediamine, however, as corrosion inhibitors it contains alkylphenoxycarboxylic acids or alkoxycarboxylic acids or semiesters of anhydrides or alkenyl dicarboxylic acids or derivatives of sarcosine and unsaturated fatty acids with the number of carbon atoms in the aliphatic chain up to 24.

The invention is explained in more detail in the following examples from 1 to 13, illustrating the composition of a multi-functional package of biocidal-stabilizing additives for the upgrading of biofuels, in particular (B100) as an alternative diesel fuel and as a biocomponent with hydrocarbon fuels in mixtures designated as B-5, B- 7, B-10, B-20, the number representing the percentage of FAME in the fuel intended for use in diesel engines and the evaluation of selected performance properties of this multi-functional package in test trials.

PL 218 043 B1

These examples are therefore not intended to limit the invention as they are merely illustrative.

P r z k ł a d 1

2.5 g of 2-n-octylisothiazolone-3 were introduced into a mixer equipped with a heating system and a circulation circuit. Then a mixture of 42.0 g of 2,6-di-tert-butyl-4-methylphenol and 49.5 g of a highly aromatic petroleum fraction with a boiling point of 220 ° C and 6.0 g of an organic monocarboxylic acid ester in the form of ethylene glycol acetate were added. an average molecular weight of 104 Daltons. The ingredients introduced into the mixer were mixed for 2 hours at the temperature of 25-35 ° C until a homogeneous, clear liquid was obtained.

P r z k ł a d 2

6.0 g of methylenebis (thiocyanate), 4.0 g of 2-thiocyanato-methylsulfenyl-1,3-benzothiazole, 0.4 g of 1,6-hexanediol nitrate and 5.0 g of a monocarboxylic acid with 12 atoms in the alkyl chain. Then, a previously prepared mixture of 26.6 g of 2,5-di-tert-butylhydroquinone and 28.0 g of a highly aromatic petroleum fraction with an aromatic content of 99.3% by weight and 30.0 g of an aliphatic ether alcohol in the form of ethoxylated butanol with an average molecular weight were added. Daltons. The ingredients introduced into the mixer were mixed for 2 hours at the temperature of 25-35 ° C until a homogeneous, clear liquid was obtained.

P r z k ł a d 3

7.5 g of methylenebis (thiocyanate), 0.5 g of 1,6-hexanediol nitrite, 5.0 g of tetrapropylene succinic acid semiester and 2.5 g of N, N-disalicydene-1 were introduced into a mixer equipped with a heating system and a circulation cycle, 2-propanediamines. Then a mixture of 20.0 g of 2,5-di-tert-butylhydroquinone and 39.5 g of a highly aromatic petroleum fraction with a boiling point of 220 ° C and 25.0 g of an aliphatic ether alcohol, in the form of ethoxylated sec-butanol of medium molecular weight, were added. 118 Daltons. The ingredients introduced into the mixer were mixed for 2 hours at the temperature of 25-35 ° C until a homogeneous, clear liquid was obtained.

P r z k ł a d 4

The product obtained as in Example 1 was introduced in an amount of 1200 mg / kg into the fuel 1, which is fatty acid methyl esters (FAME) with the properties shown in Table 1.

T a b l i c a 1

No. Property Unit Fuel 1 FAME Fuel 2 B5 1 Cetane number - 56.3 53.3 2 Density at 15 ° C kg / m ³ 882.9 838.2 3 Flash-point ° C 188 71 4 Sulfur content mg / kg <3.0 4.9 5 Coking residue in 10% distillation residue % (m / m) 0.1 0.1 6 Ash residue % (m / m) 0.002 0.001 7 Water content mg / kg 350 78.0

P r z k ł a d 5

The product obtained as in Example 2 was introduced in an amount of 300 mg / kg into the fuel 1 being fatty acid methyl esters (FAME) with the properties shown in Table 1.

P r z k ł a d 6

The product obtained as in Example 2 was introduced in an amount of 300 mg / kg into the fuel 2 with the properties shown in Table 1 being a composition of 5% (VA /) fatty acid methyl esters (FAME) and petroleum diesel.

P r z k ł a d 7

The product obtained as in Example 3 was introduced in an amount of 400 mg / kg into the fuel 1 being fatty acid methyl esters (FAME) with the properties shown in Table 1.

PL 218 043 B1

P r z k ł a d 8

The product of Example 2 in an amount of 300 mg / kg and 5 mg / kg of copper (in the form of organosoluble copper salt) were introduced into fuel 1, which is fatty acid methyl esters (FAME) with the properties shown in Table 1.

P r z k ł a d 9

The product of Example 3 in the amount of 400 mg / kg and 5 mg / kg of copper (in the form of organosoluble copper salt) were introduced into fuel 1, which is fatty acid methyl esters (FAME) with the properties shown in Table 1.

P r z k ł a d 10

Fuel 1 upgraded as in example 4 and fuel 2 upgraded as in example 6 were tested for biocidal effectiveness in a preventive test using the ASTM E 1259 method, determining the content of microorganisms in the fuel phase using the IP 385 method. The applied methodology reflects 4 refueling of fuel in the distribution chain and it is brought into contact with a contaminated aqueous phase (called a vaccine) taken from fuel refinery tanks. Table 2 shows the results of the results of the research on the effectiveness of the products in terms of microbiological protection.

T a b l i c a 2

Duration of the test [weeks] Product Material research The content of microorganisms in the fuel phase, cell / l and water phase, cell / l aerobic bacteria yeast mold fungi 2 Fuel 1 from table 1 Fuel 6200 4300 4800 Water 1.8x10 ⁷ 4.6x10 ⁶ 4.0x10 ³ Fuel 1 upgraded as in example 4 Fuel Mon 40 Mon 40 Mon 40 Water 5.5x10 ⁵ 1.0x10 ⁵ 2.2x10 ³ 8 Fuel 1 from table 1 Fuel 1.1x10 ³ 8200 9600 Water 7.3x10 ⁷ 4.8x10 ⁶ 7.4x10 ⁴ Fuel 1 upgraded as in example 4 Fuel Mon 40 Mon 40 Mon 40 Water 7800 6400 800 2 Fuel 2 from table 1 Fuel 2200 660 480 Water 1.7x10 ⁷ 3.6x10 ⁶ 3.3x10 ³ Fuel 2 upgraded as in example 6 Fuel Mon 40 Mon 40 Mon 40 Water 3200 1500 600 8 Fuel 2 from table 1 Fuel 5600 1800 1200 Water 6.3x10 ⁷ 2.4x10 ⁶ 4.7x10 ⁴ Fuel 2 upgraded as in example 6 Fuel Mon 40 Mon 40 Mon 40 Water 1400 800 Mon 40

P r x l a d 11

The fuel 1 upgraded as in example 4 and as in example 7 was subjected to the oxidation stability test according to the PN-EN 14112 standard. The test consists in passing a stream of air 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 in this parameter expressed in time units indicates the end of the induction period of the tested sample, which proves the fuel's resistance to oxidation. The results are presented in Table 3.

PL 218 043 B1

T a b l i c a 3

No. Test fuel Test result: oxidative stability [h] 1 Fuel 1 from table 1 8.5 2 Fuel 1 upgraded as in example 4 12.5 3 Fuel 1 upgraded as in example 7 15.5

P r z k ł a d 12

The fuel 1 upgraded as in examples 5, 8 and 9 was tested for oxidative stability according to the PN-EN 14112 standard. The test carried out according to the methodology described in example 11 was aimed at assessing the effectiveness of the metal deactivator. The results are presented in Table 4.

T a b l i c a 4

No. Test fuel Test result: oxidative stability [h] 1 Fuel 1 upgraded as in example 5 16.7 2 Fuel 1 upgraded as in example 8 5.9 3 Fuel 1 upgraded as in example 9 15.7

P r x l a d 13

Fuel 1 upgraded as in Example 7 and fuel 2 upgraded as in Example 6 were tested for anti-corrosion properties according to ASTM D 665A. This test is based on the assessment of the corrosion degree of a steel pin placed for 6 hours at a temperature of 40 ° C, in 300 cm ^{3 of} fuel 1 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 5.

T a b l i c a 5

No. Test fuel Test result: The degree of corrosion on the NACE scale 1 Fuel 1 from table 1 D after 1 hour 2 Fuel 1 upgraded as in example 7 B + after 6 h 3 Fuel 2 from table 1 B after 1 hour 4 Fuel 2 upgraded as in example 6 Apo 6 h

Patent claims

Claims (2)

1. A multifunctional package of biocidal and stabilizing additives, especially for biofuels, containing a biocidal substance, hydrocarbon solvent, co-solvent, oxidation inhibitor and, optionally, an organic stabilizer, characterized in that it contains a substance with biocidal activity in the amount of 0.05% (m / m) up to 25.0% (m / m), preferably from 0.1% (m / m) to 20.0% (m / m), where the biocidal substance is methylene bis (thiocyanate) or 2 -alkylisothiazolones-3 or 2-thiocyanato-methylsulfenyl-1,3-benzothiazole or their mixture, hydrocarbon solvent in the amount of 1.0% (m / m) to 90% (m / m), which is an aromatic petroleum fraction with a temperature of boiling point up to 220 ° C and / or alkylbenzenes with the number of carbon atoms in the molecule at least 9 and straight and / or branched alkyls and co-solvent in the amount of 1.0% (m / m) to 50.0% (m / m), which are branched and / or linear aliphatic alcohols with the number of carbon atoms in the molecule from 4 to 15, preferably from 4 to 13, or polyethers or polyethers or ether alcohols derivatives of monohydroxy or polyhydroxy compounds or alkylphenol ethers or polyethers with the number of carbon atoms in the alkyl substituent from 4 to 15 or esters of aliphatic alcohols with a straight and / or branched hydrocarbon chain with the number of carbon atoms in the molecule from 3 to 15, preferably 4 to 13 or ethylene glycol esters PL 218 043 B1 or propylene or ethoxylated or propoxylated aliphatic alcohols with the number of carbon atoms in the alkyl molecule from 4 to 8 and organic monocarboxylic or dicarboxylic acids or 5.7 dioxisundecane, an oxidation inhibitor in an amount from 0.5% (m / m) to 60.0% (m / m), the oxidation inhibitor being alkylated monophenols, preferably 2,6-di-tert-butyl-4-methylphenol, or alkylated bis-phenols or alkylated hydroquinones, preferably 2,5-di-tert-butylhydroquinone, or mixture and optionally a corrosion inhibitor in the amount of 0.5% (m / m) to 10.0% (m / m), which contains alkylphenoxycarboxylic acids or alkoxycarboxylic acids or semiesters of anhydrides or alkenyl dicarboxylic acids or derivatives of sarcosine and unsaturated fatty acids in the amount of carbon atoms in the aliphatic chain up to 24 and optionally an organic stabilizer in the amount of 0.05% (m / m) to 1.0% (m / m) being 1,6-hexanediol nitrate or 1,6-hexanediol nitrite and a metal deactivator in quantity and from 0.03% (m / m) to 5.0% (m / m), containing N, N-dihydrazides, preferably 1,2-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) propionyl hydrazide or N, N-disalicydene-1,2-alkenediamine, preferably N, N-disalicylidene-1,2-propanediamine. 2. The multifunctional package of biocidal-stabilizing additives, especially for biofuels, according to claim A compound according to claim 1, characterized in that the 2-n-octylisothiazolone-3 or 2-n-decylisothiazolone-3 or 2-n-undecylisothiazolone-3 or 2- (2,5,5-trimethyl ) hexylisothiazolone-3 or 2- (3,5,5-trimethyl) hexylisothiazolone-3 or 2- (2-methyl) octylisothiazolone-3 or 2- (5,7-dimethyl) octylisothiazolone-3 or 2- (8-methyl) ) nonylisothiazolone-3 or 2- (3,5,7-trimethyl) heptylisothiazolone-3 or 2- (2,8-dimethyl) nonyl-isothiazolone-3 or mixtures thereof. 3. The multifunctional package of biocidal and stabilizing additives, especially for biofuels, according to claim A process as claimed in claim 1, characterized in that the alkylated monophenols are 2-tert-butylphenol or 4-tert-butylphenol or 2,6-di-tert-butylphenol or 2,4-di-tert-butylphenol or 2-tert-butyl-4,6-dimethylphenol or 2,6-di-tert-butyl-4-ethylphenol or 2,6-di-tert-butyl-4-n-butylphenol or 2,6-di-tert-butyl-4-isobutylphenol or 2,4,6-tritert-butylphenol or 2,6-di-tert-butyl-4-methoxyphenol or 2,6-ditert-butylmethoxy-4-methylphenol or 2,6-dicyclopentyl-4-methylphenol or 2,6-octadecyl- 4-methylphenol or 2,4,6-tricyclohexylphenol or 2,6-di-tert-butyl-4-nonylphenol or 2,6-di-tert-butyl-4-octylphenol or 2,6-dinonyl-4-methylphenol or 2,6-diphenyl-4-octadecyloxyphenol or 2,5-di-tert-butyl-4-hydroxyanisole or 3,5-di-tert-butyl-4-hydroxyanisole or 3,5-di-tert-butyl-4-hydroxyphenyl stearate. 4. The multifunctional package of biocidal-stabilizing additives, especially for biofuels, according to claim A process as claimed in claim 1, characterized in that the alkylated bis-phenols are bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate or 2,2'-methylene bis (6-tert-butyl-4-methylphenol) or 2, 2'-methylene-bis (6-tert-butyl-4-ethylphenol) or 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol) or 2,2'-methylene-bis (4,6-diitert -butylphenol) or 2,2'-ethylidene-bis (4,6-diitert-butylphenol) or 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol) or 4,4'-methylene bis (2,6-di-tert-butylphenol) or 4,4'-methylene bis (6-tert-butyl-2-methylphenol) or octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. 5. The multifunctional package of biocidal-stabilizing additives, especially for biofuels, according to claim A process as claimed in claim 1, characterized in that the alkylated hydroquinones are 2,5-di-tert-butylhydroquinone or 2,6-di-tert-butylhydroquinone or 2,5-di-tert-amylhydroquinone.