PL237255B1 - Universal pack of additives to light heating oils - Google Patents

Abstract

The subject of the application is a multifunctional package of additives for light fuel oils, containing at least a combustion modifier, an additive preventing the decomposition of the additive package and a solvent, and additionally, optionally, at least one ingredient, such as a lubricity additive, a corrosion inhibitor, an oxidation inhibitor, a demulsifier, and an additive with biocidal properties. and an organic tracer soluble in fuel. This package is characterized by the fact that it contains a combustion modifier of the FBC type (Fuel Borne Catalyst) with high effectiveness, in an amount from 10.0% (m/m) to 70.0% (m/m), preferably from 30.0 % (m/m) to 50.0% (m/m), additive preventing decomposition of the additive package, in an amount from 5.0 to 25.0% (m/m), preferably from 10.0 to 15.0% (m/m), an organic solvent, which is a highly aromatic petroleum fraction in an amount from 5.0% (m/m) to 95.0% (m/m), and additionally, optionally, a lubricity additive in an amount from 10.0% ( m/m) to 60.0% (m/m), corrosion inhibitor, in an amount from 5.0% (m/m) to 25.0% (m/m), oxidation inhibitor, in an amount from 1.0 % (m/m) to 50.0% (m/m), demulsifier in an amount from 1.0% (m/m) to 20.0% (m/m), additive with biocidal properties, in an amount from 5 .0% (m/m) to 30.0% (m/m), organic tracer soluble in fuel, in amounts from 0.1% (m/m) to 10.0% (m/m). The FBC (Fuel Borne Catalyst) combustion modifier consists of: component a) in an amount from 5.0% (m/m) to 60.0% (m/m), preferably from 25.0% (m/m) to 35.0% (m/m), which are completely and unlimitedly soluble or dispersed in light fuel oil FBC catalyst precursors in the form of complexed, non-stoichiometric iron nanooxides and/or nanohydroxides, preferably trivalent iron, containing from 5 to 30% (m/m m) iron in a complex compound, component b) in an amount from 1.0% (m/m) to 30.0% (m/m), preferably from 5.0% (m/m) to 20.0% ( m/m), which is a dispersant obtained in the reaction of renewable raw materials, which are long-chain unsaturated compounds isolated from plant or animal material or biodegradable waste, unprocessed or previously purified or separated into simpler compounds or chemically modified, with maleic anhydride, with maintaining such a molar ratio of reactants that from 1.0 to 2.0 moles of maleic anhydride are used per 1.0 mol of renewable raw material, preferably from 1.0 to 1.2 moles of maleic anhydride per 1.0 mol of renewable raw material, with the reaction is carried out without the use of a solvent, in a periodic manner, with continuous, intensive stirring, for 3 to 10 hours, preferably 4 to 6 hours, while maintaining a temperature from 160°C to 240°C, preferably from 190°C to 225°C, and the long-chain unsaturated compounds used are 10-undecenoic acid or (Z)-9-hexadecaenoic acid or (Z)-9-octadecaenoic acid or (E)-9-octadecaenoic acid or (Z)-9-octadecaenoic acid or (E)-11-octadecaenoic acid or 3,7-dimethyl-6-octadecaenoic acid or 11-(3-cyclopentyl-)-undecenoic acid or 11-(3-cyclopentyl-)-undecenoic acid or 13-(3) -cyclopentyl-)-tridecenoic acid or (Z)-13-docosenoic acid or (Z)-15-tetracosenoic acid or (Z,Z)-9,12-octadecadienoic acid or (Z,Z)-9,12-octadecadienoic acid or (Z,Z,Z)-9,12,15-octadecatrienoic acid or (Z,Z,Z)6,9,12-octadecatrienoic acid or (EEE)-9,12,15-octadecatrienoic acid or (EEE )-9,11,13-octadecatrienoic acid or (R)-12-hydroxy-(Z)-9-octadecenoic acid or dimers or trimers thereof or glycerides thereof or ester derivatives thereof or amide derivatives thereof, which ester or amide derivatives thereof obtained by reaction with primary monoalcohols with the number of carbon atoms in the molecule from 1 to 8 or with primary amines with the number of carbon atoms in the molecule from 1 to 6 and the number of nitrogen atoms in the molecule from 1 to 2 or any mixture thereof and component c) in amounts from 5.0% (m/m) to 80.0% (m/m), preferably from 10.0% (m/m) to 65.0% (m/m), which is an organic solvent that is a hydrocarbon solvent with a boiling point of up to 220°C under standard conditions or an aliphatic linear and/or branched alcohol having a molecular number of carbon atoms from 8 to 13 or an ether or polyether or an ether alcohol such as an ethoxylated monoalcohol or a polyoxyethylene alkylphenol or any mixture thereof.

Description

Description of the invention

TECHNICAL FIELD

The subject of the invention is a multifunctional package of additives for light fuel oils, containing a combustion modifier stabilized with a dispersant, intended for use in energy-efficient central heating boilers, steam boilers, industrial furnaces and technological furnaces.

STATE OF THE ART

Highly energy-efficient boilers are equipped with low-emission burners operating at pressures from 700 to 2000 kPa and swirl nozzles that atomize the fuel and at the same time create a fuel-air mixture. High temperatures in the core zone of the flame with an insufficient amount of air right next to the spray nozzles cause fuel cracking processes, during which soot and sediment and coke precursors are formed. At the same time, the high temperature of the nozzle tips, exceeding 300 ° C, causes that under these temperature and pressure conditions, the fuel undergoes thermal degradation before it is atomized, and the sediment precursors contained in such fuel under the influence of temperature and pressure, heat-pressure flocculation to adhesive sediments, accumulating on the surface of the channels of high pressure spray nozzles and obstructing the proper atomization of the fuel.

Sludge and coke accumulating in the channels of high-pressure nozzles reduce the flow of fuel dosed to the combustion chamber, which reduces the boiler's energy efficiency and increases the emission of soot, carbon monoxide and unburned hydrocarbons.

The unfavorable phenomena related to the processes of atomization and combustion of fuel can be prevented by using packages of conditioners containing detergent-dispersing additives, keeping the tips of fuel atomizers clean. Moreover, the aforementioned packages usually include components facilitating the ignition of fuel oil, modifiers improving the combustion process, lubricating additives modifying friction in fuel pump elements, anti-corrosive additives, demulsifiers and others.

Additives or packages of additives to light fuel oils improving their operational properties are the subject of many patents.

Patent description PL 187379 describes a new generation of light fuel oil additive package which contains, mixed with each other at a temperature from 10 ° C to 120 ° C, preferably from 20 ° C to 50 ° C: an active substance with detergent-dispersing properties, in the amount of 5.0% (m / m) to 50.0% (m / m), and / or a substance facilitating the ignition of fuel oil, in the amount of 5.0% (m / m) to 70.0% ( m / m), and / or stabilizer, in the amount of 0.1% (m / m) to 5.0% (m / m), and / or substances improving the combustion of fuel oil and / or a substance that reduces the emission of toxic components of exhaust gases, in the amount of 5.0% (m / m) to 70.0% (m / m), and / or substances improving the lubricating properties of fuel oils, and / or being friction modifiers, in the amount of 5.0% ( m / m) up to 60.0% (m / m), and / or a demulsifier, in an amount from 0.1% (m / m) to 5.0% (m / m), and / or a substance with anti-corrosive properties , in an amount from 0.1% (m / m) to 5.0% (m / m), and / or anti-aging and / or antioxidant substances, in an amount from 0.1% (m / m) to 10, 0% (m / m), and / or a substance with biocidal properties, in an amount from 1.0% (m / m) to 50.0% (m / m), and / or an organic marker that allows identification of fuel oil, in an amount from 0.1% (m / m) to 10.0% (m / m).

From the patent description P.365967 a multifunctional package of fuel oil additives is known, which contains, mixed with each other at a temperature of 10 ° C to 50 ° C, a modifier of the combustion process of hydrocarbon fuels and / or biofuels, in the amount of up to 1.0% (m / m) up to 70% (m / m) and / or an additive facilitating the ignition of fuel oil, in the amount of 2.0% (m / m) to 70% (m / m) and / or detergent-dispersant additive, in the amount of from 5.0% (m / m) to 50.0% (m / m) and / or a solubilizer, in an amount from 0.1% (m / m) to 20% (m / m) and / or a lubricating additive , in an amount from 1.0% (m / m) to 50.0% (m / m) and / or demulsifier and / or foam inhibitor, in an amount from 0.1% (m / m) to 5.0% (m / m) and / or a corrosion inhibitor in the amount of 0.1% (m / m) to 5.0% (m / m) and / or a substance with biocidal properties in the amount of 0.1% (m / m) / m) up to 30.0% (m / m) and / or an oxidation inhibitor in an amount from 0.1% (m / m) to 5.0% (m / m) and / or a marker enabling identification of fuel oil, in an amount from 0.1% (m / m) to 20.0% (m / m) and a hydrocarbon solvent, with the process modifier combustion of hydrocarbon fuels and / or biofuels are complex organosoluble iron salts, preferably trivalent iron, containing from 1.0 to 5.5 mol of iron / kg of complex compound and possibly organic compounds of metals of the II group of the periodic table, preferably magnesium and / or calcium, completely and unlimitedly soluble in fuel oils.

PL 237 255 B1

From US 5,525,127 and EP 0662507 a package of additives is known to improve the operational properties of hydrocarbon distillate fuel intended for use in furnaces equipped with evaporating burners. According to these patents, the additive package contains (methylcyclopentadienyl) manganese tricarbonyl (MCMT) as a combustion modifier, ashless succinimide dispersant, aliphatic dicarboxylic acid, N-type metal deactivator, N'-disalicylidene-1,2-propenediamine, preferably alkoxylated alkylphenediamine ethoxylated alkylphenol, demulsifier, tertiary amine, preferably alkylcyclodialkylamine stabilizer and solvent with a final boiling point not greater than 300 ° C.

According to US patent 8852298, the use of additive compositions for hydrocarbon fuels, such as diesel oil, light fuel oil, GTL (gas-to-liquid), BTL (biomass-to-liquid), CTL ( : coal-to-liquid), containing ferrocene in an amount up to about 35 mg iron per liter of fuel, and manganese tricarbonyl (methylcyclopentadienyl) manganese in an amount up to about 36 mg manganese per liter of fuel, significantly reduces the formation of deposits in the combustion chambers, which extends the working cycle of the furnace, burner or injectors.

According to the patent application US 2012/0102822 a package of additives for hydrocarbon fuels is known, which comprises a sol containing particles of at least one inorganic metal compound and at least one organometallic compound stabilized in a suitable hydrocarbon carrier. The metallic compounds are metal complexes selected from the elements of Groups VIII-XI of the Periodic Table of the Elements, preferably platinum, cobalt, nickel, copper, gold and rhodium, most preferably palladium. The use of the package improves the combustion process of fuels in internal combustion engines, heating chambers and jet engines.

US Patent No. 7,524,338 describes a diesel and fuel oil additive package containing an organometallic combustion catalyst containing iron, cerium, calcium compounds or mixtures thereof, organic nitrate and a dispersant that reduces the emission of particulate matter emitted by diesel engines and furnaces fired with fuel oil.

In the patent application CN 103509616 a package of refining additives for fuel oil is claimed, containing salts of higher fatty acids of rare earth metals and compounds of metals such as cobalt, manganese, iron; dispersant being a product of the synthesis of polyisobutylene succinic anhydride with polyamines; a combustion enhancing additive which may be a ferric or calcium salt of higher fatty acids and a solvent which may be an alkylbenzene, benzene, toluene, xylene or diesel fuel. The advantage of the described package is that when dosed in a weight ratio from 1: 500 to 1: 3000 to fuel oil, it reduces the emission of solid particles by 40-70 percent, improves the combustion efficiency of fuel oil by 10-25 percent, is cheap to produce and is not requires modification of existing fuel supply systems.

In the patent application US 2006/0000140 there is presented an additive package containing stabilized with fatty acids, especially oleic acid, iron, cerium oxides or mixtures thereof, whose task is to reduce the emission of harmful substances. The package also includes: a lubricant improving agent and a detergent-dispersant to prevent turbidity of the refined fuel and sedimentation at low temperatures.

From the patent application US 2013/0183628 a composition of enriching additives is known to improve the combustion economy of hydrocarbon fuels and to enable the use of "heavier" fractions in devices adapted to burn light heating oil. The package includes: corrosion inhibitors, antistatic additives, dyes, additives reducing the cloud point, detergents and the main component, which is a combustion modifier containing iron, manganese, calcium atoms or their mixture.

The patent application WO 2008/073017 discloses the composition of an additive package for crude oil and hydrocarbon fuels aimed at improving the performance properties of fuels upgraded with this package. It consists of at least one ferric additive in the form of ferric carboxylate and / or ferrous formate and an organic or inorganic compound of another metal, e.g. calcium. In addition, the package contains at least one anionic, cationic and / or nonionic surfactant, a stabilizer and a dispersant.

From the patent description US 7,585,336 the composition of the additive package for diesel oil and light fuel oil is known, which reduces the amount of soot and solid particles released in the combustion process. The package includes a solution or dispersion of a soluble metal compound or a metal carboxylate, e.g. iron, detergent additive, depressant, anti-foaming agent.

PL 237 255 B1

From the description of the patent application P.404521 there is known a multifunctional additive for fuel oils containing a combustion modifier in the amount of 5.0% (m / m) to 15.0% (m / m) and an organic solvent in the amount of 5.0% (m / m) to 94.0% (m / m) and preferably a co-modifier of the combustion process in an amount of 2.0% (m / m) to 12.0% (m / m) and preferably an active substance with detergent and dispersants in the amount of 2.5% (m / m) to 20.5% (m / m) and optionally an additive ensuring the stability of the composition in the amount of 0.5% (m / m) to 2.5% (m / m) ) and optionally a fuel-soluble organic marker in an amount of 0.1% (m / m) to 10.0% (m / m). As a modifier of the combustion process, complex, non-stoichiometric nanooxides and / or nano-hydroxides and / or nano-iron oxy-hydroxides, preferably trivalent iron, containing from 1.0 to 5.5 moles of iron / kg of a complex compound, dispersed in a mixture of an aliphatic solvent and a high-molecular, unsaturated derivative are used. carboxylic acid with a number of carbon atoms in the molecule from 9 to 19, and organic complexes and / or metal salts of block s and / or block d of the periodic table of at least one of the metals such as potassium and / or calcium and / or magnesium and / or strontium and / or manganese and / or cobalt and / or platinum and / or copper and / or ruthenium and / or osmium and / or zircon and / or palladium and / or vanadium and / or zinc, and as substances with detergent-dispersant properties, modified alkenyl succinimide-amides are used, obtained in the process of acylation of polyalkylene polyamines with alkenyl succinic anhydride and subjected to the process thermal conditioning under controlled pressure and temperature conditions. As an additive ensuring the stability of the composition, alkenyl succinic acid derivatives with an average molecular weight from 500 to 1200 Da, preferably from 600 to 900 Da, were used in the multifunctional additive according to the application P.404521; the fuel-soluble organic marker is a molecular marker and / or a marker which is an azophenol derivative and / or a coumarin derivative and / or a hydroxyanthraquinone derivative; the solvent used was a petroleum fraction with the number of carbon atoms in the molecule at least 9 and a final boiling point up to 350 ° C under normal conditions, and optionally linear and / or branched aliphatic alcohols with the number of carbon atoms in the molecule from 8 to 13 and / or ethers and / or polyethers and / or etheralcohols derivatives of monoalcohols and / or alkylphenol ethers and / or polyethers.

From the patent application P.398294 there is known a multifunctional package of additives for diesel fuels, containing modified alkenyl succinimide-amides as an active substance with detergent-dispersant properties, and also at least a demulsifier, a foam inhibitor and an organic solvent, and possibly an additive improving the electrostatic conductivity of the fuel and a marker, which is characterized by the fact that it contains from 5.0% (m / m) to 80.0% (m / m) of the active substance with detergent-dispersant properties in the form of modified alkenyl succinimide-amides, obtained in the process of thermal conditioning of acylation products of polyalkylene polyamines alkenyl succinic anhydride and / or a wetting agent, in the amount of 1.0% (m / m) to 70.0% (m / m), and / or an ashless combustion modifier and / or an ignition aid modifier and / or an additive increasing the number of cetane, in the amount of 5.0% (m / m) to 50.0% (m / m) and / or friction modifiers, in the amount of 5.0% ( m / m) up to 60.0% (m / m) and / or oxidation inhibitors in the amount from 1.0% (m / m) to 50.0% (m / m) and / or metal deactivators in the amount of from 1.0% (m / m) to 10.0% (m / m) and demulsifiers, in an amount from 1.0% (m / m) to 30.0% (m / m) and foam inhibitors, in the amount from 1.0% (m / m) to 20.0% (m / m) and / or corrosion inhibitors in the amount from 0.5% (m / m) to 10.0% (m / m) and / or a substance with biocidal properties, in an amount from 0.1% (m / m) to 30.0% (m / m) and / or an additive improving the electrostatic conductivity of the fuel, in the amount of 0.05% (m / m) up to 5.0% (m / m) and / or a fuel-soluble marker in an amount from 0.05% (m / m) to 5.0% (m / m) and an organic solvent being a petroleum fraction and / or containing oxygen. The wetting agent used in the package according to application P.398294 is: alkoxylated, preferably poly (oxyethyl) and / or poly (oxypropyl) alcohols and / or alkylphenols with an alkyl substituent containing not less than 9 carbon atoms, obtained by a multi-stage oxyalkylation ethylene and / or propylene oxide of alcohols and / or alkylphenols, the average molecular weight of the poly (oxyethyl) and / or poly (oxypropyl) alcohols and / or alkylphenols being 300 to 3000 Daltons, preferably 500 to 2000 Daltons, as an ashless modifier of the combustion process and / or a modifier facilitating ignition and / or an additive increasing the cetane number, alpha, beta-dinitropolybutenes and / or alpha, beta-dinitropolyisobutanes and / or hydroxynitropolyisobutanes and / or hydroxynitropolyisobutanes and / or esters of nitric acid and / or or nitrous straight and / or branched primary and / or secondary alcohols containing from 3 to 15 carbon atoms per molecule, nat In general, synthetic saturated acids are used as friction modifiers

Monocarboxylic acids with the number of carbon atoms in the alkyl chain from 6 to 12, preferably branched-chain, and / or esters and / or amides and / or unsaturated fatty acids with the number of carbon atoms in the aliphatic chain from 18 to 24, and / or products of their esterification and / or amidization and / or semesters of alkenyl succinic anhydrides and / or dicarboxylic acids with an average molecular weight from 200 to 600 Dalton and / or semiamides and / or amide esters of alkenyl succinic anhydrides and / or dicarboxylic acids with an average molecular weight from 200 up to 600 Daltons. The following are used as oxidation inhibitors in the package according to the application P.398294: 2,6-di-tert-butyl-4-methylphenol and / or 2,6-di-tert-butyl-4-ethylphenol and / or 2,6-di-tert-butyl-4 -butylphenol and / or 2,6-di-tert-butyl-4-isobutylphenol and / or 2-tert-butyl-4,6-dimethylphenol and / or 2,4,6-ditert-butylphenol and / or 2,6-ditert -butyl-4-methoxyphenol and / or 2,5-di-tert-butylhydroquinone and / or 2,5-diitert-amylhydroquinone and / or 4,4'-methylene bis-2,6-di-tert-butylphenol and / or 2, 6-di-tert-butylphenol and / or 2,4-ditert-butylphenol and / or 2,2'-ethylidene-4,6-di-tert-butylphenol and / or 2,6-di-tert-butyl-4-nonylphenol and / or 2 , 6-di-tert-butyl-4-octylphenol, while the demulsifiers are polyoxyethylated and / or polyoxypropylated alkylphenol derivatives with an alkyl substituent and a straight and / or branched chain structure containing from 6 to 28 carbon atoms and / or ether alcohols, preferably primary alcohols with the number of carbon atoms in the molecule from 8 to 18 and the number of ether groups from 10 to 25. As inhi Corrosion bitors are used in the package according to application P.398294: alkylphenoxycarboxylic acids and / or alkoxycarboxylic acids and / or semi-amides and / or semi-esters of anhydrides and / or alkenyl dicarboxylic acids, preferably with a branched structure of an alkenyl substituent, with an average molecular weight from 250 to 500 Daltons and / or reaction products of unsaturated fatty acids having a number of carbon atoms in the aliphatic chain from 12 to 24 and sarcosine and / or its derivatives; the substance with biocidal properties is methylene bis (thiocyanate) and / or 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-tert-octylisothiazolone-3 and / or 2-decylisothiazolone-3 and / or 2-tridecyl-isothiazolone-3 and / or 2-octadecylisothiazolone-3 and / or 2-cyclopropylisothiazolone-3 and / or 2-cyclohexylisothiazolone-3 and / or 2-cyclopentylisothiazolone-3 and / or 2-phenylisothiazolone-3 and / or 2-phenoxyethylisothiazolone-3 and / or 2-benzylisothiazolone-3 and / or 2- (thiocyanomethylthio) benzothiazole; as metal deactivators, N, N-dihydrazides are used, preferably 1,2-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) propionhydrazide and / or N, N-disalicylidene-1,2-alkylene diamine, preferably N, N-disalicylidene-1,2-propenediamine; polysiloxane ether copolymers and / or organomodified polysiloxanes which are soluble in hydrocarbons and which are insoluble in the water phase are used as foam inhibitors. As the fuel-soluble tracer, a molecular tag and / or an azophenol derivative and / or coumarin derivative and / or a hydroxyanthraquinone derivative are used. The organic solvent used is a petroleum fraction, preferably aromatic, with a number of carbon atoms in the molecule of at least 9 and a final boiling point of up to 350 ° C under normal conditions, and / or linear and / or branched aliphatic alcohols with the number of carbon atoms in the molecule from 8 to 13, and / or ethers and / or polyethers and / or ether alcohols derivatives of monoalcohols and / or alkylphenol ethers and / or polyethers.

From the patent application P.405712 there is known a multifunctional detergent-dispersant additive for energy-saving diesel fuels, which contains from 5.0% (m / m) to 80.0% (m / m) of a surfactant with detergent-dispersing properties in the form of alkenyl succinimides with an ammonium cation and a methyl carbonate and / or methyl oxalate anion, from 10.0% (m / m) to 70.0% (m / m) lubricity modifier and from 5.0% (m / m) to 30.0% (m / m) of an oxidation inhibitor and from 2.0% (m / m) to 60.0% (m / m) of an organic solvent which is a petroleum fraction, preferably aromatic, with a number of carbon atoms in the molecule at least 9 and boiling point up to 350 ° C under normal conditions. The alkenyl succinimide surfactants with an ammonium cation and a methyl carbonate and / or methyl oxalate anion used in the additive composition are acylation products of dimethylaminopropylamine with alkenyl succinic anhydride with an average molecular weight of 750 to 2500 Daltons. Moreover, the multifunctional detergent-dispersant additive may optionally contain a corrosion inhibitor in the amount of 1.0% (m / m) to 20.0% (m / m), a demulsifier and / or a foam inhibitor in an amount of 1.0% (m / m). m) up to 20.0% (m / m), a substance with biocidal properties in an amount from 0.5% (m / m) to 30.0% (m / m), a metal deactivator in an amount from 1.0% ( m / m) to 10.0% (m / m). The multifunctional additive according to the application P.405712 contains as a lubricity modifier synthetic saturated monocarboxylic acids with the number of carbon atoms in the branched alkyl chain from 6 to 12, unsaturated fatty acids with the number of carbon atoms in the aliphatic chain from 18 to 24, preferably fatty acids such as oleic acid , linolenic, linoleic, acid oil

Tallow, soybean oil acid, rapeseed oil acid; as an oxidation inhibitor it contains 2,6-di-tert-butyl-4-methylphenol or 2,6-di-tert-butyl-4-ethylphenol or 2,6-di-tert-butyl-4-butylphenol or 2,6-di-tert-butyl-4- isobutylphenol or 2-tert-butyl-4,6-dimethylphenol or 2,4,6-tritert-butylphenol or 2,6-di-tert-butyl-4-methoxyphenol or 2,5-diitert-butyl hydroquinone or 2,5- ditert-amylhydroquinone or 4,4'-methylene-bis- (2,6-di-tert-butylphenol) or 2,6-ditert-butylphenol or 2,4-ditert-butylphenol or 2,2'-ethylidene-bis- (4 , 6-di-tert-butylphenol) or 2,6-di-tert-butyl-4-nonylphenol or 2,6-di-tert-butyl-4-octylphenol, or mixtures thereof; as a corrosion inhibitor, the package comprises alkylphenoxycarboxylic acids, ethoxylated nonylphenol, reaction products of unsaturated fatty acids having the number of carbon atoms in the aliphatic chain from 12 to 24, and sarcosine or mixtures thereof; as a demulsifier and / or foam inhibitor, the package contains polyoxyalkylenated or polypropoxylated alkylphenol derivatives with an alkyl substituent of a straight or branched structure containing from 6 to 28 carbon atoms or etheralcohols, preferably derivatives of primary alcohols with the number of carbon atoms in the molecule from 8 to 18 and the number of ether groups from 10 to 25, or polysiloxane-ether copolymers or organomodified polysiloxanes soluble in hydrocarbons and insoluble in water phase as substances with biocidal properties, the package contains methylene-bis (thiocyanate) or 2-methylisothiazolone-3 or 2-ethylisothiazolone-3 or 2 -propylisothiazolone-3 or 2-isopropylisothiazolone-3 or 2-butylisothiazolone-3 or 2-isobutylisothiazolone-3 or 2-tertbutylisothiazolone-3 or 2-hexylisothiazolone-3 or 2-octylisothiazolone-3 or 2-decylisothiazolone-3 or 2-decylisothiazolone -3 or 2-tridecylisothiazolone-3 or 2-octadecylisothiazolone-3 or 2-cyclopropylisothiazo 3-lon-3 or 2-cyclohexylisothiazolone-3 or 2-cyclopentylisothiazolone-3 or 2-phenylisothiazolone-3 or 2-phenoxyethylisothiazolone-3 or 2-benzylisothiazolone-3 or 2- (thiocyanomethylthio) benzothiazole, or any mixture thereof; contains as metal deactivator N, N-dihydrazides, preferably 1,2-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) propionhydrazide and / or N, N-disalicylidene-1,2-alkylene diamine, preferably N, N -disalicylidene-1,2-propenediamine.

From the Polish patent application P.410190, not published on the date of filing the application of the present invention, there is known a stabilized combustion modifier of high efficiency for light fuel oils, improving the combustion of carbon particles and hydrocarbons, which contains from 5.0% (m / m) to 60.0% (m / m) completely and unlimitedly soluble or dispersible in light fuel oil FBC catalyst precursors in the form of complexed, non-stoichiomesteric nanoxides and / or nanohydroxides and / or iron oxyhydroxides, containing 5 to 30% (m / m) of iron in a complex compound, an organic dispersant in the amount of 1.0% (m / m) to 30.0% (m / m), being a mixture of aliphatic and / or aromatic mono- and / or dicarboxylic acids with carbon atoms in molecules from 4 to 24, preferably from 10 to 22 and optionally esters and / or semesters derived from mono- and / or dicarboxylic acids with the number of carbon atoms in molecules from 4 to 24 and linear alcohols or cyclic monohydroxy and / or polyhydroxy with a content of carbon atoms in molecules from 1 to 9 and the content of hydroxyl groups in molecules from 1 to 4 and / or amides and / or imides and / or amideimides, derived from mono- and / or dicarboxylic acids with the number of carbon atoms in molecules from 4 to 24 and amines or aliphatic polyamines with the content of nitrogen atoms in molecules from 1 to 6 and / or hydroxyamides and / or hydroxyimides, which are derivatives of mono- and / or dicarboxylic acids with numbers of carbon atoms in molecules from 4 to 24 and amino alcohols with the content of hydroxyl groups in molecules 1 to 4 and the content of nitrogen atoms in molecules 1 to 6 and an organic solvent in the amount of 5.0% (m / m) to 80.0% (m / m) ), being a hydrocarbon solvent with a boiling point of up to 220 ° C under normal conditions, or a linear and / or branched aliphatic alcohol with the number of carbon atoms in molecules from 8 to 13, or an ether or polyether or ether alcohol a derivative of a monoalcohol and an alkylphenol ether or polyether, or a mixture thereof.

From the description of the Korean patent application KR20100013654 a combustion modifier is known, which reduces the emission of nitrogen oxides and exhibits good properties in the combustion of carbon particles. Combustion modifier consists of nanoparticles (size 20-30 nm) of divalent and trivalent iron compounds dispersed in oleic acid (surfactant) and kerosene: Fe (OH) 2, Fe (OH) 3, FeO, Fe2O3 and Fe3O4.

The main objective of the invention is to obtain a multifunctional package of additives for light fuel oils, characterized by improved storage stability and increased effectiveness in reducing the emission of harmful substances - especially solid particles and unburned hydrocarbons, compared to the known packages used for light fuel oils,

And also containing components that provide the appropriate performance properties to the light fuel oil refined with this package.

SUMMARY OF THE INVENTION

It has surprisingly been found that the multifunctional additive package for light fuel oils according to the present invention has such desirable properties, comprising a combustion modifier stabilized with a dispersant obtained with the use of renewable raw materials and at least an additive preventing decomposition of the additive package and a solvent.

The multi-functional light fuel oil additive package according to the present invention, containing at least a dispersant stabilized combustion modifier, an additive preventing decomposition of the additive package and an organic solvent which is a highly aromatic petroleum fraction, and further optionally at least one component such as a lubricity additive, a corrosion inhibitor, an oxidation inhibitor. , demulsifier, additive with biocidal properties, fuel-soluble organic marker, characterized by the fact that it contains a combustion modifier of the FBC (Fuel Borne Catalyst) type with high efficiency, stabilized with a dispersant, in the amount of 10.0% (m / m) to 70.0% (m / m), preferably from 30.0% (m / m) to 50.0% (m / m), additive preventing decomposition of the additive package, in the amount of 5.0% (m / m) to 25.0% (m / m), preferably from 10.0% (m / m) to 15.0% (m / m) and an organic solvent, which is a highly aromatic petroleum fraction, in an amount of 5.0% (m / m) / m) up to 95.0% (m / m) and further optionally lubricity additive, in the amount of 10.0% (m / m) to 60.0% (m / m), corrosion inhibitor, in the amount of 5.0% (m / m) to 25.0% (m / m) ), oxidation inhibitor, in an amount from 1.0% (m / m) to 50.0% (m / m), demulsifier, in an amount from 1.0% (m / m) to 20.0% (m / m) m), additive with biocidal properties, in the amount of 5.0% (m / m) to 30.0% (m / m), organic tracer soluble in fuel, in the amount of 0.1% (m / m) to 10.0% (m / m).

In the multifunctional package of additives for light fuel oils according to the invention, a combustion modifier stabilized with a dispersant obtained with the use of renewable raw materials is used, improving the combustion of carbon particles and hydrocarbons, which contains:

- component a) in an amount from 5.0% (m / m) to 60.0% (m / m), preferably from 25.0% (m / m) to 35.0% (m / m), which are completely and unlimitedly soluble or dispersible in light fuel oil precursors of FBC catalysts in the form of complexed, non-stoichiometric nanoxides and / or nanohydroxides and / or nanohydroxides of iron, preferably trivalent iron, containing from 5% (m / m) to 30% (m / m) ) iron in a complex compound,

- component b) in an amount of from 1.0% (m / m) to 30.0% (m / m), preferably from 5.0% (m / m) to 20.0% (m / m), which is a dispersant obtained by reacting renewable raw materials, which are long-chain unsaturated compounds, isolated from plant or animal material or from biodegradable waste, unprocessed or previously treated or separated into simpler compounds or subjected to chemical modifications, with maleic anhydride, maintaining the molar ratio of the reactants that 1.0 to 2.0 moles of maleic anhydride per 1.0 mole of renewable feedstock, preferably 1.0 to 1.2 moles of maleic anhydride per 1.0 mole of renewable feedstock, and the reaction is carried out without the use of a solvent, batchwise, with continuous intensive stirring, for 3 to 10 hours, preferably 4 to 6 hours, while maintaining a temperature from 160 ° C to 240 ° C, preferably from 190 ° C to 225 ° C, and as long-chain unsaturated compounds, acid 10- undecenoic acid or (Z) -9-hexadecanoic acid or (Z) -9-octadecanoic acid or (E) -9-octadecanoic acid or (Z) -6-octadecanoic acid or (E) -11-octadecanoic acid or 3 acid, 7-dimethyl-6-octadecenoic acid or 11- (3-cyclopentyl -) - undecenoic acid or 11- (3-cyclopentyl -) - undecenoic acid or 13- (3-cyclopentyl -) - tridecenoic acid or (Z) -13 acid -docosic or (Z) -15-tetracosoic acid or (Z, Z) -9,12-octadecadienoic acid or (Z, Z) -9,12-octadecadienoic acid or (Z, Z, Z) -9.12 acid , 15-octadecatrienoic acid or (Z, Z, Z) -6,9,12-octadecatrienoic acid or (E, E, E) -9,12,15-octadecatriene acid or (E, E, E) -9 acid, 11,13-octadecatrienoic or (R) -12-hydroxy- (Z) -9-octadecenoic acid or their dimers or trimers or their glycerides or their ester derivatives or their amide derivatives, which ester or amide derivatives are obtained by reaction with primary monoalcohols with the number of carbon atoms in the molecule from 1 to 8 or with primary amines with the number of carbon atoms in the molecule from 1 to 6 and the number of nitrogen atoms in molecules 1 to 2, or any mixture thereof, and

- component c) in an amount of from 5.0% (m / m) to 80.0% (m / m), preferably from 10.0% (m / m) to 65.0% (m / m), which is an organic solvent, which is a hydrocarbon solvent with a boiling point of up to 220 ° C under normal conditions, or a linear and / or branched aliphatic alcohol with the number of carbon atoms in molecules from 8 to 13, or an ether or a polyether or an etheral

Alcohol, such as ethoxylated monoalcohol or polyoxyethylene alkylphenol, or any mixture thereof.

The percentage of iron, preferably trivalent, as complex compounds contained in the FBC precursors is based on the total weight of the combustion modifier.

The percentages of the individual components of the stabilized combustion modifier, i.e. a), b) and c), are based on the total weight of the stabilized combustion modifier.

For the purposes of the present invention, mixtures of paraffins and naphthenes containing mainly 11 to 12 carbon atoms per molecule and traces of aromatic hydrocarbons, free of polycyclic aromatics, heavy metals and chlorinated hydrocarbons may be used as the organic solvent, which is a hydrocarbon solvent.

For the purposes of the present invention, as an ether, polyether or ether alcohol such as ethoxylated monoalcohol or polyoxyethylene alkylphenol, compounds having an amount of carbon atoms in the molecule from 2 to 18 and an amount of ether groups from 1 to 6 and no more than one aromatic ring and one hydroxyl group may be used. in the molecule.

The dispersant used in the above formulation, obtained with the use of renewable raw materials, is characterized, in the presence of co-catalysts containing metal compounds from groups 1 to 12 of the periodic table of the elements, by higher stability compared to other known FBC additives. The high efficiency FBC (Fuel Borne Catalyst) combustion modifier for light fuel oils used in the multi-functional package according to the present invention, stabilized with a dispersant obtained with the use of renewable raw materials, is the subject of a separate patent application filed on the date of filing the application of the present invention.

The multi-functional high-performance additive package for light fuel oils according to the invention as an additive to prevent decomposition of the additive package contains alkenyl succinic acid derivatives with an average molecular weight from 500 to 1200 Da, preferably from 600 to 900 Da, such as esters or amides or imides that obtained by reaction with primary or secondary alcohols or amines having a number of carbon atoms in the molecules from 2 to 8, preferably from 3 to 5.

The multifunctional package of highly effective additives for light fuel oils according to the invention as an organic solvent, being a highly aromatic petroleum fraction, contains solvents with a boiling point range from 180 to 220 ° C, containing more than 99% (m / m) of aromatic hydrocarbons with the number of carbon atoms in the molecule mainly from 10 to 11 and not containing polycyclic aromatic compounds, heavy metals and chlorinated hydrocarbons.

The multifunctional high-performance additive package for light fuel oils according to the invention as a lubricating additive contains synthetic saturated monocarboxylic acids with the number of carbon atoms in the alkyl chain from 6 to 12, preferably branched-chain, or their esters or their amides or unsaturated fatty acids with the number of atoms carbon in the aliphatic chain from 18 to 24 or products of their esterification or amidization, with the use of esters and amides obtained by reaction with primary or secondary alcohols or amines with the number of carbon atoms in molecules from 2 to 8, preferably from 3 to 5, or contains monoesters of alkenyl succinic anhydrides or dicarboxylic acids with an average molecular weight of 200 to 600 Dalton or monoamides or amide esters of alkenyl succinic anhydrides or dicarboxylic acids with an average molecular weight of 200 to 600 Dalton, or any mixture thereof.

The multi-functional high-performance additive package for light fuel oils according to the invention as a corrosion inhibitor contains alkylphenoxycarboxylic acids or alkoxycarboxylic acids or monoamides or monoesters of anhydrides or alkenyl dicarboxylic acids with an average molecular weight of 250 to 500 Daltons or reaction products of unsaturated fatty acids with the number of carbon atoms in the aliphatic chain from 12 to 24 and sarcosine, or any mixture thereof.

The multi-functional high-performance additive package for light fuel oils according to the invention as an oxidation inhibitor contains 2,6-di-tert-butyl-4-methylphenol or 2,6-di-tert-butyl-4-ethylphenol or 2,6-di-tert-butyl-4 -butylphenol or 2,6-ditert-butyl-4-isobutylphenol or 2-tert-butyl-4,6-dimethylphenol or 2,4,6-tritert-butylphenol or 2,6-ditert-butyl-4-methoxyphenol or 2 , 5-diitert-butyl-hydroquinone or 2,5-diitert-amylhydroquinone or 4,4'-methylene-bis- (2,6-ditert-butylphenol) or 2,6-di-tert-butylphenol or 2,4-ditert- butylphenol or 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol) or 2,6-di-tert-butyl-4-nonylphenol or 2,6-di-tert-butyl-4-octylphenol, or any mixture thereof.

PL 237 255 B1

The multi-functional package of high-performance additives for light fuel oils according to the invention as a deemulsifier comprises polyoxyalkylenated alkylphenol derivatives with an alkyl substituent of a straight or branched structure, containing in the substituent and in oxyalkylene molecules a total of 12 to 28 carbon atoms or etheralcohols, preferably derivatives of primary alcohols with the number of carbon atoms in the molecule from 8 to 18 and the number of ether groups from 10 to 25, or any mixture thereof.

The multi-functional high-performance additive package for light fuel oils according to the invention contains, as an additive with biocidal properties, methylene bis (thiocyanate) or 2-methylisothiazolone-3 or 2-ethylisothiazolone-3 or 2-propylisothiazolone-3 or 2-isopropylisothiazolone-3 or 2-butylisothiazolone-3 or 2-isobutylisothiazolone-3 or 2-tert-butylisothiazolone-3 or 2-hexylisothiazolone-3 or 2-octylisothiazolone-3 or 2-tertoctylisothiazolone-3 or 2-decylisothiazolon-3 or 2-triazolone-3 or 2-triazolonecyl octadecylisothiazolone-3 or 2-cyclopropylisothiazolone-3 or 2-cyclohexylisothiazolone-3 or 2-cyclopentylisothiazolone-3 or 2-phenylisothiazolone-3 or 2-phenoxyethylisothiazolone-3 or 2-benzylisothiazolone-3 or 2-benzylisothiazolone-3 or their benzomethyl mixture.

The multi-functional high-performance additive package for light fuel oils according to the invention is characterized in that as the fuel-soluble organic tag it contains a molecular tag or an alkyl derivative of azophenol or coumarin or hydroxyanthraquinone in which the alkyl group contains a linear or branched hydrocarbon chain with an amount of carbon atoms from 2 to 6, or any mixture thereof.

The invention is further explained in the following examples from 1 to 19, showing the composition of a multi-functional package of high-performance additives for light fuel oils and the evaluation of selected properties of this package in laboratory and bench tests. However, it should be understood that these examples are not to be construed as limiting the invention as they are illustrative only.

EXAMPLES

P r z k ł a d 1

103.2 g of dried and ground mortar maleic anhydride of 95% purity and 264 g of oleic acid were introduced into the reactor equipped with a reflux condenser cooled with water at a temperature of 65 ° C. The mixture was heated to 220 ° C and this temperature was maintained for 5 hours. The obtained crude product was distilled at 180 ° C under reduced pressure of 15 mm Hg. The obtained product was filtered. In the IR spectrum of the pure product, characteristic bands were identified, at a wavelength of 1860 cm ^-1 and 1740 cm ^-1 , originating from deforming vibrations of the five-membered saturated anhydride ring.

P r z k ł a d 2

103.2 g of dried and ground in a mortar maleic anhydride of 95% purity and 296.5 g of a mixture of methyl esters of monocarboxylic acids of various chain lengths (from C16 to C24) were introduced into the reactor equipped with a reflux condenser, cooled with water at a temperature of 65 ° C. obtained in the process of transesterification of fat obtained from refining rapeseed. The mixture was heated to 200 ° C and this temperature was maintained for 5 hours. The obtained crude product was distilled at 180 ° C under reduced pressure of 15 mm Hg. The obtained product was filtered. In the IR spectrum of the pure product, characteristic bands were identified, at a wavelength of 1860 cm ^-1 and 1740 cm ^-1 , resulting from the characteristic deformation vibrations of the five-membered saturated anhydride ring.

P r z k ł a d 3

30 g of hydrated iron II sulfate VI and 45 g of hydrated iron III sulfate VI, 150 ml of water were introduced into the reactor equipped with a reflux condenser, an anchor stirrer, a heating system and a dropping funnel. The contents were stirred at room temperature until the salt was completely dissolved. Then, while stirring, the contents of the reactor were heated to a temperature of 60 ° C, and after the temperature was established, 15% R-R ammonia was added dropwise until the pH was 7.5. A mixture of 15.0 g of the product of Example 1, 105.0 g of toluene and 90.0 g of an aliphatic petroleum fraction with a boiling range of 180-210 ° C was added to the resulting suspension. The contents of the reaction mixture were heated to 70 ° C with constant stirring and this temperature was maintained for 5 hours. After this time, the obtained mixture was transferred to a separating funnel, and the aqueous layer was separated from the organic layer containing the mixture of valuable iron II and III compounds. The crude organic fraction was fed to a reactor equipped with a reflux condenser, an anchor stirrer,

Heating system and dropping funnel. The fraction was heated to 60 ° C, and then 200.0 g of a 3.0% hydrogen peroxide solution was added dropwise with vigorous stirring. After completion of the dropwise addition, the contents of the reactor were held at 70 ° C and stirred for 1 hour. It was then put into a separating funnel and water was separated from the organic layer. Water was azeotropically distilled from the organic fraction and the precipitate was filtered off.

P r z k ł a d 4

30 g of hydrated iron II sulfate VI and 45 g of hydrated iron III sulfate VI, 150 ml of water were introduced into the reactor equipped with a reflux condenser, an anchor stirrer, a heating system and a dropping funnel. The contents were stirred at room temperature until the salt was completely dissolved. Then, while stirring, the contents of the reactor were heated to a temperature of 60 ° C, and after the temperature was established, 15% R-R ammonia was added dropwise until the pH was 7.5. A mixture consisting of 19.4 g of the product of Example 2, 105.0 g of toluene and 90.0 g of an aliphatic petroleum fraction with a boiling range of 180-210 ° C was added to the resulting suspension. The contents of the reaction mixture were heated to 70 ° C with constant stirring and this temperature was maintained for 5 hours. After this time, the obtained mixture was transferred to a separating funnel, and the aqueous layer was separated from the organic layer containing the mixture of valuable iron II and III compounds. The crude organic fraction was fed to a reactor equipped with a reflux condenser, an anchor stirrer, a heating system, and a dropping funnel. The fraction was heated to 60 ° C, and then 200.0 g of a 3.0% hydrogen peroxide solution was added dropwise with vigorous stirring. After completion of the dropwise addition, the contents of the reactor were held at 70 ° C and stirred for 1 hour. It was then put into a separating funnel and water was separated from the organic layer. Water was azeotropically distilled from the organic fraction and the precipitate was filtered off.

P r z k ł a d 5

The combustion modifier was produced according to the method described in the patent application P.410190 for comparative purposes. 30 g of hydrated iron II sulfate VI and 45 g of hydrated iron III sulfate VI, 150 ml of water were introduced into the reactor equipped with a reflux condenser, an anchor stirrer, a heating system and a dropping funnel. The contents were stirred at room temperature until the salt was completely dissolved. Then, while stirring, the contents of the reactor were heated to a temperature of 60 ° C, and after the temperature was established, 15% R-R ammonia was added dropwise until the pH was 7.5. A mixture of 8.0 g of olein and 8 g of 10-undecenoic acid, 105.0 g of toluene and 90.0 g of an aliphatic petroleum fraction with a boiling range of 180-210 ° C was added to the resulting suspension. The contents of the reaction mixture were heated to 70 ° C with constant stirring and this temperature was maintained for 5 hours. After this time, the obtained mixture was transferred to a separating funnel, and the aqueous layer was separated from the organic layer containing the mixture of valuable iron II and III compounds. The crude organic fraction was fed to a reactor equipped with a reflux condenser, an anchor stirrer, a heating system, and a dropping funnel. The fraction was heated to 60 ° C, and then 200.0 g of a 3.0% hydrogen peroxide solution was added dropwise with vigorous stirring. After completion of the dropwise addition, the contents of the reactor were held at 70 ° C and stirred for 1 hour. It was then put into a separating funnel and water was separated from the organic layer.

P r z k ł a d 6

30 g of the product of Example 3, 3 g of tetrapropylene succinic acid tert-butyl ester with an average molecular weight of 350 Daltons and 10 g of highly aromatic petroleum fraction with a boiling range of 180-220 ° C were introduced into a mixer equipped with a heating system and circulation circulation. The product was heated to 50 ° C and stirred until a homogeneous, clear liquid was obtained.

P r z k ł a d 7

40 g of the product of Example 4, 5 g of n-propyl tetrapropylene succinic acid ester with an average molecular weight of 350 Daltons and 40 g of highly aromatic petroleum fraction with a boiling range of 180-220 ° C were introduced into a mixer equipped with a heating system and circulation circulation. The product was heated to 50 ° C and stirred until a homogeneous, clear liquid was obtained.

P r z k ł a d 8

30 g of the product of Example 5, 5 g of n-butyl tetrapropylene succinic acid ester with an average molecular weight of 350 Daltons and 40 g of highly aromatic petroleum fraction with the temperature range were introduced into a mixer equipped with a heating system and circulation circulation.

PL 237 255 Β1 boiling point 180-220 ° C. The product was heated to 50 ° C and stirred until a homogeneous, clear liquid was obtained.

Example 9

To 43 g of the product from Example 6 was introduced 57 g of the previously prepared mixture consisting of 26 g of saturated monocarboxylic acid with branched hydrocarbon chain containing 8 carbon atoms and molecular weight of 144 Dalton, 5 g of N-acylsarcosine - oleic acid derivative, 16 g 2 , 6-di-tert-butyl-4-methylphenol and 10 g of highly aromatic petroleum with a boiling point of 225 ° C. The product was heated to 50 ° C and stirred until a homogeneous, clear liquid was obtained.

Example 10

28.5 g of the previously prepared mixture consisting of 12.5 g of a saturated dicarboxylic acid with a polyalkenyl substituent and a weight equal to 440 Dalton, 2.5 g of an unsaturated fatty acid reaction product with a molecular weight of 230 was introduced to 21.5 g of the product from Example 7. Daltons and polyamines with a molecular weight of 170 Daltons, 8 g of 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol) and 5.5 g of a highly aromatic petroleum fraction with a boiling point of 225 ° C. The product was heated to 50 ° C and stirred until a homogeneous, clear liquid was obtained.

Example 11

To 42 g of the product from Example 8 were introduced 28 g of the previously prepared mixture consisting of 23 g of the monoester being the reaction product of alkenylsuccinic anhydride of 600 Daltons and nonyl alcohol, 2.5 g of N-acylsarcosine - oleic acid derivative, 8 g of 2.6- di-tert-butyl-4-methoxyphenol and 10 g of highly aromatic petroleum with a boiling point of 225 ° C. The product was heated to 50 ° C and stirred until a homogeneous, clear liquid was obtained.

Example 12

The product of Example 9 was introduced in an amount of 500 mg / kg into a light fuel oil with the properties shown in Table 1.

Table 1

Physicochemical properties of light fuel oil.

Property Unit Findings 1 Calorific value MJ / kg 45.6 2 Fractional composition to 250 ° C distilled to 350 ° C has distilled % (V / V) % (W 61.0 95.3 3 Density at 15 ° C kg / m ³ 826.7 4 Sulfur content mg / kg 50 5 Flash-point "C 66 6 Oxidation resistance g / m ³ 3.1 7 Lubricity, corrected wear scar diameter (WS 1.4) at 6O ° C pm 566

PL 237 255 Β1

Example 13

The product of Example 10 was introduced in an amount of 500 mg / kg into a light fuel oil with the properties shown in Table 1.

Example 14

The product of example 11 was introduced in an amount of 500 mg / kg into a light fuel oil with the properties shown in Table 1.

Example 15

Light fuel oil enriched as in the examples 12, 13, 14 was tested for compatibility of the package with the fuel. The refined light fuel oils were stored at the temperature of 80 ° C for the period of 7 days. Each sample was visually inspected daily for turbidity, deposits, and delamination. Samples, in which no changes were found in relation to the visual inspection of the samples at the beginning of the test, were qualified as treated with a fully compatible additive package. The results are presented in Table 2.

Table 2

Test results for the compatibility of additive packages with light fuel oil.

Test fuel Test result ^ Compatibility test at 80 ° C 2 Light fuel oil from example 12 compatible 3 Light fuel oil from example 13 compatible 4 Light fuel oil from example 14 compatible

Example 16

Light fuel oil enriched as in examples 12, 13, 14 was burned in a steam boiler with a rated power of 80 kW of the Viessmann Parmornat Triplex type, powered by light fuel oil and equipped with a GA-40T + digital exhaust gas analyzer. The emission of pollutants was tested. The concentration of hydrocarbons in the exhaust gas was determined by gas chromatography in accordance with the PN-89 / Z-040014 standard. The results of the tests for the emission of harmful exhaust components are presented in Table 3.

Table 3

The results of the emission tests of harmful exhaust components.

Emission component Emission Light fuel oil from table 1 Light fuel oil from example 12 Light fuel oil from example 13 Light fuel oil from example 14 WHAT 0.0019 -73.7 -52.6 60.0 NOx 0.0161 '4.3 7.7 0.0 Hydrocarbons 0.2600 -61.5 -60.0 -61.5

Example 17

The enriched light fuel oil, as in the examples 12, 13, 14, was tested for its lubricating properties according to the PN-EN ISO 12156-1 standard. The principle of the test is to excite a small, top-loaded steel ball with high horizontal vibration frequency on a steel surface immersed in the tested fuel at a temperature of 60 ° C. After the test is completed, the diameter of the defect is measured. The test results for lubricating properties are shown in Table 4.

PL 237 255 Β1

Table 4

Test results for lubricating properties according to PN-EN ISO 12156-1.

Test fuel Test result ^: Lubricity, corrected wear mark diameter (WS 1.4) at 60 ° C, gm 1 Light heating oil from table 1 566 2 Light fuel oil from example 12 385 3 Light fuel oil from example 13 366 4 Light fuel oil from example 14 380

Example 18

Light fuel oil upgraded as in Examples 12, 13, 14 was tested for anti-corrosive properties according to ASTM D 665A. The test consists in assessing the corrosion degree of a steel pin placed for 5 hours in an intensively mixed environment of 300 cm ^{3 of} light fuel oil and 30 cm ³ of distilled water. The mandrel corrosion grade is performed according to the NACE TM-02-75 scale, which has a rating range of A to E, with the A score being no corrosion. The test results for anti-corrosive properties are presented in Table 5.

Table 5

Test results for anti-corrosion properties according to ASTM D 665A.

Test fuel Test result ^ The degree of corrosion on the NACE scale 1 Light fuel oil from table 1 B 2 Light fuel oil from example 12 B ⁺⁺ 3 Light fuel oil from example 13 B ^{t +} 4 Light fuel oil from example 14 AND

Example 19

Light fuel oil enriched as in examples 12, 13, 14 was subjected to oxidation resistance test according to PN ISO 12205 standard. This test consists in assessing the total sludge content in an accelerated aging test. The evaluation criterion for light fuel oil is a total sediment content of not more than 25 g / m ³ . The results of the oxidation resistance tests are presented in Table 6.

PL 237 255 Β1

Table 6

The results of the tests of resistance to oxidation according to PN ISO 12205.

Test fuel Total sediment content, mg / m ³ 1 Light fuel oil from table 1 3.1 2 Light fuel oil from example 12 2.7 3 Light heating oil from example 13 2.5 4 Light fuel oil from example 14 2.7

Patent claims

Claims (4)

1. Multifunctional package of additives for light fuel oils containing at least: I. Fuel Borne Catalyst type combustion modifier, which includes: - component a) which are completely and unlimitedly soluble or dispersible in light fuel oil precursors of Fuel Borne Catalyst catalysts in the form of complexed, non-stoichiometric nanoxides and / or nanohydroxides and / or nanohydroxides of trivalent iron, containing from 5 to 30% (m / m) of iron in a complex relationship; - component b) which is a dispersant; and - component c), which is an organic solvent, being a hydrocarbon solvent with a boiling point of up to 220 ° C under normal conditions, or a linear and / or branched aliphatic alcohol with the number of carbon atoms in molecules from 8 to 13, or an ether or a polyether or ether alcohol selected from ethoxylated monoalcohol and polyoxyethylene alkylphenol; II. additive preventing decomposition of the additive package, which are derivatives of alkenyl succinic acid, with an average molecular weight from 500 to 1200 Da, selected from esters or amides or imides, obtained by reaction with primary or secondary alcohols or amines with the number of carbon atoms in molecules from 3 to 5; and III. organic solvent, being a highly aromatic petroleum fraction, containing solvents with a boiling range of 180 to 220 ° C, containing more than 99% (m / m) of aromatic hydrocarbons, with a number of carbon atoms in the molecule predominantly from 10 to 11 and no polycyclic aromatic compounds , heavy metals and chlorinated hydrocarbons; and further optionally at least one component selected from the following: IV. lubricity additive, which are synthetic saturated monocarboxylic acids with the number of carbon atoms in the branched alkyl chain from 6 to 12, or their esters or their amides or unsaturated fatty acids with the number of carbon atoms in the aliphatic chain from 18 to 24 or their esterification or amidization products, where esters and amides obtained by reaction with primary or secondary alcohols or amines with the number of carbon atoms in molecules from 3 to 5 or which are monoesters of alkenyl succinic anhydrides or dicarboxylic acids with an average molecular weight of 200 to 600 Dalton or monoamides or amide esters of anhydrides alkenyl succinic or dicarboxylic acids with an average molecular weight from 200 to 600 Daltons; V. corrosion inhibitor, which are alkylphenoxycarboxylic acids or alkoxycarboxylic acids or monoamides or monoesters of anhydrides or alkenyl dicarboxylic acids with an average molecular weight of 250 to 500 Daltons or non-acid reaction products Fatty acids having a number of carbon atoms in the aliphatic chain from 12 to 24 and sarcosine; VI. an oxidation inhibitor which is 2,6-di-tert-butyl-4-methylphenol or 2,6-di-tert-butyl-4-ethylphenol or 2,6-di-tert-butyl-4-butylphenol or 2,6-di-tert-butyl-4 -isobutylphenol or 2-tert-butyl-4,6-dimethylphenol or 2,4,6-tritert-butylphenol or 2,6-di-tert-butyl-4-methoxyphenol or 2,5-diitert-butyl-hydroquinone or 2,5 -ditert-amylhydroquinone or 4,4'-methylene-bis- (2,6-di-tert-butylphenol) or 2,6-di-tert-butylphenol or 2,4-di-tert-butylphenol or 2,2'-ethylidene-bis- ( 4,6-di-tert-butylphenol) or 2,6-di-tert-butyl-4-nonylphenol or 2,6-di-tert-butyl-4-octylphenol; VII. deemulsifier, which are polyoxyalkylenated derivatives of alkylphenols with an alkyl substituent of a straight or branched structure, containing in the substituent and in oxyalkylene molecules a total of 12 to 28 carbon atoms or etheralcohols, derivatives of primary alcohols with the number of carbon atoms in the molecule from 8 to 18 and the number of ether groups from 10 to 25; VIII. an additive with biocidal properties, which is methylene bis (thiocyanate) or 2-methylisothiazolone-3 or 2-ethylisothiazolone-3 or 2-propylisothiazolone-3 or 2-isopropylisothiazolone-3 or 2-butylisothiazolone-3 or 2-isobutylisothiazolone-3 2-tert-butylisothiazolone-3 or 2-hexylisothiazolone-3 or 2-octylisothiazolone-3 or 2-tertoctylisothiazolone-3 or 2-decylisothiazolone-3 or 2-tridecylisothiazolone-3 or 2-octadecylisothiazolone-3 or 2-octadecylisothiazolon-3 or 2-octadecylisothiazolon-3 or 2-octadecylisothiazolone-3 cyclohexylisothiazolone-3 or 2-cyclopentylisothiazolone-3 or 2-phenylisothiazolone-3 or 2-phenoxyethylisothiazolone-3 or 2-benzylisothiazolone-3 or 2- (thiocyanomethylthio) benzothiazole; IX. a fuel-soluble organic tag which is a molecular tag or an alkyl derivative of azophenol or coumarin or hydroxyanthraquinone in which the alkyl group comprises a linear or branched hydrocarbon chain with carbon atoms from 2 to 6; characterized by: I. Fuel Borne Catalyst combustion modifier, in an amount from 10.0% (m / m) to 70% (m / m), which includes, based on the total mass of the stabilized combustion modifier: - component a) in an amount from 5.0% (m / m) to 60.0% (m / m), - component b) in an amount from 1.0% (m / m) to 30.0% (m / m), which is a dispersant obtained by reacting renewable raw materials which are long-chain unsaturated compounds, isolated from plant or animal material or from biodegradable waste , unprocessed or previously purified or separated into simpler compounds or chemically modified, with maleic anhydride, with the molar ratio of the reactants being such that 1.0 to 2.0 moles of maleic anhydride are used for 1.0 mole of renewable raw material, with the reaction is carried out without the use of a solvent, batchwise, under constant, intensive stirring, for 3 to 10 hours, maintaining a temperature from 160 ° C to 240 ° C, and 10-undecenoic acid or (Z) -9-hexadecanoic acid or (Z) -9-octadecanoic acid or (E) -9-octadecanoic acid or (Z) -6-octadecanoic acid or (E) -11-octadecanoic acid or 3,7- dimethyl-6-octa decaenoic acid or 11- (3-cyclopentyl -) - undecenoic acid or 11- (3-cyclopentyl -) - undecenoic acid or 13- (3-cyclopentyl -) - tridecenoic acid or (Z) -13-docosenoic acid or (Z ) -15-tetracosenoic acid or (Z, Z) -9,12-octadecadienoic acid or (Z, Z) -9,12-octadecadienoic acid or (Z, Z, Z) -9,12,15-octadecatrienoic acid or acid (Z, Z, Z) -6,9,12-octadecatrienoic acid or (E, E, E) -9,12,15-octadecatrienoic acid or (E, E, E) -9,11,13-octadecatriene acid or (R) -12-hydroxy- (Z) -9-octadecenoic acid or their dimers or their trimers or their glycerides or their ester derivatives or their amide derivatives, which ester or amide derivatives are obtained by reaction with mono-atomic primary alcohols carbon in molecule 1 to 8 or with primary amines having a carbon number of carbon atoms in molecule 1 to 6 and a number of nitrogen atoms in molecule 1 to 2; and - component c) in an amount from 5.0% (m / m) to 80.0% (m / m); II. additive preventing decomposition of the additive package, in the amount of 5.0% (m / m) to 25.0% (m / m); PL 237 255 B1 III. an organic solvent in the amount of 5.0% (m / m) to 95.0% (m / m); and in addition, possibly: IV. lubricity additive, in an amount from 10.0% (m / m) to 60.0% (m / m); V. corrosion inhibitor, in an amount from 5.0% (m / m) to 25.0% (m / m); VI. an oxidation inhibitor, in an amount from 1.0% (m / m) to 50.0% (m / m); VII. demulsifier, in an amount from 1.0% (m / m) to 20.0% (m / m); VIII. additive with biocidal properties, in the amount of 5.0% (m / m) to 30.0% (m / m); IX. organic marker, soluble in fuel, in the amount from 0.1% (m / m) to 10.0% (m / m). 2. Multifunctional package of additives for light fuel oils according to claim 1, characterized in that it contains component I in an amount from 30.0% (m / m) to 50.0% (m / m) and component II in an amount from 10.0% (m / m) to 15.0% % (m / m). 3. Multifunctional light fuel oil additive package according to claim A process as claimed in claim 1 or 2, characterized in that component I comprises: - component a) in an amount from 25.0% (m / m) to 35.0% (m / m), - component b) in an amount from 5.0% (m / m) to 20.0% (m / m), and - component c) in an amount from 10.0% (m / m) to 65.0% (m / m). 4. Multifunctional package of additives for light fuel oils according to claim A method as claimed in claim 1 or 3, characterized in that component b) contained in component I was obtained by reacting renewable raw materials with maleic anhydride, with the molar ratio of the reactants being such that 1.0 to 1 is used for 1.0 mol of renewable raw material, 2 moles of maleic anhydride, 4 to 6 hours, maintaining the temperature from 190 ° C to 225 ° C.