PL238362B1 - Universal pack of additives to heating oils - Google Patents

Description

TECHNICAL FIELD

The subject of the invention is a universal additive package intended for the refining of fuel oils used in particular in highly energy-efficient central heating boilers, steam boilers, industrial furnaces and technological furnaces.

STATE OF THE ART

In the conditions of cold start-up of boilers fed with fuel oils, especially when heavy fuel oils are used, the atomization of fuels is not appropriate. Large droplets with a relatively small evaporation surface dominate. Low temperatures during start-up are not conducive to intense soot burning, which significantly increases the total amount emitted to the atmosphere. In order to reduce the amount of soot formation, for example, metallic oxidizing nanocatalysts and substances with surfactant properties that reduce surface tension and improve fuel atomization are used.

In the soot oxidation process, mainly additives containing metal compounds (especially oxides) are used, whose electrons with the highest energy are in the ground state in the d orbitals (these metals can be present in many degrees of oxidation). Compounds composed of elements of this type have the ability to create complex complex systems and are easily subject to redox reactions, which is particularly important in the case of additives modifying the combustion process. Combustion modifiers currently used are made of compounds containing mainly the following metals: Ce, Fe, Pt, Zn.

High temperatures in the flame core zone 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. High pressure as well as high temperature of the burner nozzles, exceeding 250 ° C, cause that under these temperature and pressure conditions, the fuel undergoes thermal degradation before it is atomized, and the sediment precursors contained in such fuel are subject to thermal and pressure flocculation to adhesive sediments under the influence of temperature and pressure. by accumulating on the surface of the channels of high-pressure spray nozzles and preventing the proper atomization of the fuel.

Accumulation of coke deposits on the burner elements may lead to malfunctions in the operation of the boilers. Deposits interfere with the fuel flow, changing the size of the dose and worsening the quality of its atomization. As a result of the unfavorable phenomena described above, the emission of harmful exhaust gas components may increase, fuel consumption may increase, and in extreme cases the burner may fail. Therefore, it is necessary to effectively counteract the above-mentioned phenomena.

The deposits and carbon deposits formed under the influence of temperature are partially or completely melted, which increases their tendency to stick and stick to the metal internal surfaces of heating installations. This phenomenon significantly reduces the efficiency of power devices, as well as increases the risk of high-temperature corrosion.

The unfavorable phenomena related to the exploitation of heating oils, intended for use in particular in highly efficient energy devices, are also favored by the tendency of fuel oils to oxidize, delaminate, as well as to precipitate resins, asphaltenes, paraffins, etc. The most important factors that may cause the loss of stability of heavy fuel oil are blending with light components, exposure to elevated temperatures, and contact with oxygen, which causes oxidation of some unsaturated and resinous asphalt compounds.

The consequence of the poor stability of heavy fuel oils is the precipitation and agglomeration of sludge during their storage and operation, and thus the disturbance of the proper storage conditions through the accumulation of sludge at the bottom of the tanks, clogging of filters and installation lines, preventing the fuel flow to the burner, the occurrence of heterogeneity in the form of fuel stratification, which results in significant fluctuations in the physicochemical properties of the fuel, especially viscosity and ignition temperature.

The unfavorable phenomena related to the exploitation of fuels can be prevented, inter alia, by using active substances with detergent-dispersing and antioxidant-stabilizing properties. The action of this type of substances is aimed at preventing oxidation and aging processes in the entire volume of fuel, preventing its delamination, as well as dispersing existing asphaltenes, resins, paraffins and other agglomerates of organic origin during its processing.

Storage. On the other hand, the action of detergent additives is directed mainly against the formation, accumulation and deposition of sediments and carbon deposits during fuel combustion processes, especially on the nozzles of sprayers. These deposits adversely affect the degree and range of the atomized fuel stream, and thus change the established, optimal conditions for the fuel combustion process. The action of detergent-dispersing substances is to create a protective layer on the metal surface preventing the formation of sediment precursors.

Chemical compounds used as detergent-dispersing active substances are organic compounds which, due to their structure, are highly polar, which on the one hand gives them detergent properties, and on the other allows the formation of a protective layer on the metal surface.

The basic feature of the structure of organic compounds used as detergent and / or dispersant additives is the presence of nitrogen atoms in their molecules. Both the content of total nitrogen, expressed in% by mass, and the content of the so-called basic nitrogen, expressed as mg KOH / g.

The groups of organic compounds that are most often used as detergent and / or dispersant active substances are: amides and imides derived from high molecular weight organic acids, Mannich bases, carbamates and carbamate derivatives, alkylphenols, polyetheramines and polybutenamines.

As antioxidant-stabilizing additives, usually tert-butylalkylphenols and tert-alkylhydroquinones are used, which bind free radicals and stop chain reactions.

In the patent application WO 2007/007191, an additive composition for fuels such as diesel fuel, marine fuel, light and heavy fuel oil is presented, allowing to reduce the content of soot and ash in flue gas. The composition consists of an additive containing a metal compound selected from iron, manganese, calcium and cerium compounds or a mixture thereof in an amount from 3 ppm to 30,000 ppm, an organic compound selected from bicyclic monoterpenes, substituted bicyclic monoterpenes, adamantanes, propylene carbonate or a mixture of these compounds in amounts from 100 ppm to 700,000 ppm.

The patent application CN 101705123 presents an environmentally friendly and energy-saving package of additives for heavy fuel oil, which reduces the viscosity of the refined oil, eliminates black smoke generated during its combustion and reduces the formation of coke on the nozzles, which reduces the cost of servicing boilers. Containing 8-20 parts by weight of amphoteric surfactants such as 2-ethylhexyl succinulfonate; 10-20 parts by weight of a combustion aid such as methyl tert-butyl ether, ethyl tert-butyl ether or mixtures thereof; 20-35 parts by weight of a dispersant such as polyvinylpyrrolidone; 3-15 parts by weight of a corrosion inhibitor such as N, N-bis-salicylate-1,2-propylenediamine and 20-50 parts by weight of water.

From the patent application CN 102559306, a package of additives for heavy fuel oil is known, the advantage of which is that it improves the stability of the oil during its storage, reduces the amount of deposits formed on the fuel injection nozzles into the boiler, reduces its viscosity and the amount of black smoke produced, improves the effect of spraying and protects the fittings against corrosion. The package includes 10-30 parts by weight of a surfactant, which is a mixture of fatty acid esters, polyethylene glycol and polyoxyethylene alkylphenol ethers; 15-60 parts by weight of a combustion enhancing additive which is a mixture of polyisobutylenes and polyethylene alcohols; 10-55 parts by weight of a dispersant consisting of a mixture of polyamines with alkenyl succinic ether; 1-8 parts by weight of a corrosion inhibitor mixture of sulfonic lignin derivatives, N, N-bis-salicylate-1,2-propylenediamine and polyalcohols; 20-50 parts by weight of water.

CN patent application 103509616 discloses a package of enriching additives for diesel fuel and heavy fuel oil, consisting of salts of higher fatty acids of rare earth metals and metals such as cobalt, manganese, iron; a dispersant which is a product of the synthesis of polyisobutylene succinic anhydride with polyamines; a combustion enhancing additive which may be an iron 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.

PL 238 362 B1

From CN application 103695055 there is known a package of additives for heavy fuel oils consisting of 10 to 35 parts by weight of a demulsifier consisting of a mixture of polyethylene polyamine polyether, propylene glycol and acetic acid; from 8 to 20 parts by weight of an undefined surfactant; 10 to 20 parts by weight of a combustion catalyst such as methyl tert-butyl ether, ethyl tert-butyl ether or mixtures thereof; from 20 to 35 parts by weight of a stabilizer / dispersant such as polyvinylpyrrolidone; from 3 to 15 parts by weight of a corrosion inhibitor such as N, N-bis-salicylate-1,2-propylenediamine and from 20 to 50 parts by weight of water. The advantage of this package is, according to the description, that the oil refined with it can be stored for up to five months without losing its properties. It reduces the viscosity of the oil, which facilitates its dosing into the boiler and mixing with air.

Patent application CN 103897755 describes a dispersant for high-bituminous marine fuel consisting of 10-50 parts by weight of esters of carboxylic acids having a chain of 10 to 16 carbon atoms; 20-60 parts by weight of alkylbenzenesulfonic acid in which the alkyl group contains from 12 to 18 carbon atoms; 5-20 parts by weight of ethoxylated fatty alcohols containing from 10 to 18 carbon atoms and 10-30 parts by weight of a solvent. The advantage of the present dispersant is the ability to prevent asphaltenes from precipitating from the marine fuel, low production costs and easy dosing to the finished fuel.

The patent application EP 1752516 discloses a dispersant which can be used for motor fuels such as diesel fuel, unleaded gasoline, ethyline as well as light and heavy fuel oils with an asphaltene content of up to 30% by weight. The dispersant consists of the reaction products of polyisobutylene succinic anhydrides with an average molecular weight from 500 to 5000 Dalton and polyamines containing from 2 to 6 nitrogen atoms and a weight of not less than 350 Dalton.

Patent description US 6,335,550 describes a fuel oil dispersant obtained by reacting, in a molar ratio of 4: 3 to 1:10, an alkenyl derivative of a monounsaturated dicarboxylic acid containing from 4 to 10 carbon atoms, with a polyamine containing in its chain from 3 to 6 nitrogen atoms. The dispersant is used in an amount from 10 ppm by mass to 400 ppm by mass, based on the active substance.

US Patent No. 7,524,338 describes a package of additives for diesel oil and fuel oils consisting of an organometallic iron-containing combustion catalyst (in an amount of 6 to 7% by weight), cerium (in an amount of 5 to 6% by weight), calcium (in an amount of 2, 5 to 3 wt.%) Or mixtures thereof in the form of an aliphatic acid salt, an organic nitrate (e.g., amyl nitrate, isoamyl nitrate, isooctyl nitrate or mixtures thereof) and a dispersant that reduces particulate emissions from diesel engines and fuel oil fired furnaces. The dispersant used in the package belongs to the group of alkylamines, arylamines or arylamides. The organometallic catalyst content in the additive package is 2 to 30% by weight, the organic nitrate is 50 to 70% by weight, and the dispersant is 5 to 15% by weight, and the fuel package dosing is 1 to 10 g / dm ^{3 of} fuel.

US patent application 2014/0000156 discloses a heavy fuel oil additive package consisting of an organosoluble compound containing any one metal selected from: calcium, barium, manganese or iron in an amount of 25 to 55 wt.%, 15 to 25 wt.% Alcohol containing 1 up to 5 carbon atoms, 10 to 20% by weight of light petroleum distillates, and 2 to 8% by weight of non-ionic detergents, e.g. polyethylene glycol, fatty acid ester. Calcium alicolobenzene sulphonates with 8 to 20 carbon atoms in the alkyl chain were used both as dispersant and combustion catalyst. The package dosage is 0.001 to 1 part of the package for 100 parts by mass of fuel.

The authors of EP 2173838 describe the use of a nitrogen containing dispersant additive to improve the oxidation stability of biofuels such as diesel, light and heavy fuel oil. This additive includes products obtained by reacting polyisobutylene succinic acid derivatives containing 12 to 200 carbon atoms in the polyisobutylene chain and molecular weight from 500 to 2800 with polyethylene amines containing 1 to 8 amine groups in the chain.

The authors of the patent application US 2005/0223627 describe the use of the reaction product of a succinic anhydride derivative with a primary amine as an additive increasing the thermo-oxidative stability of hydrocarbon fuels. The succinic anhydride derivative contains an alkyl or alkylene chain with a length of 4 to 29 carbon atoms, the amine contains 1 to 5 amino groups, the molar ratio of the reactants is 1: 0.2 to 1: 1. The additive is used in an amount of 1 to 200 ppm.

PL 238 362 B1

The authors of patent applications EP 2302020, WO 2009/016400 and WO2008GB050626 disclosed that the use of a dispersing-stabilizing additive in the amount of 500 to 20,000 ppm ensures excellent thermo-oxidative stability of such hydrocarbon fuels as: biodiesel, diesel oil, gasoline, aviation fuel, marine fuel, heating oil , heavy fuel oil, GTE (gas-to-liquid) fuel, CTL (coal-to-liquid) fuel, BTL (biomass-to-liquid) fuel and OTL (oil sands-to-liquid) fuel. The described dispersing and stabilizing additive is the reaction product of a substituted succinic acid derivative, with a molecular weight of 500 to 1500, and polyamines from the group: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethyleneheptamine, dimethylaminopropylamine, and aminoethyl mixtures thereof.

Patent application US 2002/0142923 describes a composition of antioxidants containing in its composition the reaction products of ortho-tert-butylphenol (OTBP), 2,6-di-tert-butylphenol (DTBP) with formaldehyde in an organic solvent in the presence of a catalyst. This composition is further characterized by a low level of 2,6-di-tert-butylphenol and ortho-tert-butylphenol, a trace level of 2,4,6-tritert-butylphenol. The composition can be used for jet fuels, gasoline, heating oils and diesel fuels.

The authors of US patent application US 2007/0154608 have disclosed a polymer in the chain of two or more aromatic ring monomers substituted with at least one tert-butyl group or a substituted or unsubstituted n-alkoxycarbonyl group. This substance has excellent antioxidant properties when used in petroleum products (e.g. gasoline, kerosene, diesel, heating oil, propane, jet fuel).

The authors of the patent application US 2007/0106059 presented a method of obtaining a macromolecular substance (cexyl-1,6-bis [N- (4-hydroxyphenyl) -3- (2,6-di-tert-butyl-4-hydroxyphenyl) amide]) with excellent antioxidant properties and high thermal resistance, as well as polymers based on them. Also presented are antioxidant additives for liquid hydrocarbon fuels containing products of these syntheses.

Patent applications US 2009/0300974, WO 2013/007738, US 2007/0197412 disclose additive compositions containing 2,6-di-tert-butyl-4-methylphenol (BHT) and / or tert-butylhydroquinone (TBHQ) as antioxidant additives to fuels .

The patent description PL 189615 discloses the composition of a fuel oil containing from 200 to 680 ppm of a performance additive composition, consisting of detergents in an amount of 50-150 ppm, such as succinimide, demulsifying agents in the amount of 1-3 ppm, such as such as oxyalkylated alkylphenol resins, acylated polyglycols, sodium arylsulfonates, 200-400 ppm 2-ethylhexyl nitrate combustion agents and / or 5-15 ppm iron or magnesium salts of higher fatty acids based on iron or magnesium as well as anti-corrosive agents in an amount of 2-5 ppm, an aromatic solvent and optionally dyes and markers.

The description of the application P.404521 discloses the composition of a multifunctional additive for fuel oils containing from 6.0% (m / m) to 10.0% (m / m) of the combustion process modifier, from 4.0% (m / m) to 8 , 0% (m / m) of a co-modifier of the combustion process, preferably an active substance with detergent-dispersing properties in the form of alkenyl succinimide-amides in an amount from 3.0% (m / m) to 10.0% (m / m) and an additive providing composition stability in the amount of 0.8% (m / m) to 1.4% (m / m) and / or a fuel-soluble organic marker in the amount of 0.1% (m / m) to 10.0% ( m / m) and an organic solvent, being a petroleum fraction and / or containing oxygen. The specification discloses that the combustion modifier used is complexed, non-stoichiometric nano-oxides and / or nano-hydroxides and / or nano-iron oxy-oxides, preferably trivalent iron, containing from 1.0 to 5.5 moles of iron / kg of complex compound, and an organic dispersant, which is a high molecular weight an unsaturated carboxylic acid derivative having a carbon number of 9 to 19 in a hydrocarbon solvent. In the same description, complexes and / or metal salts of block si / or block d of the periodic table of at least one of the metals potassium and / or calcium and / or magnesium and / or strontium and / or manganese and / or cobalt were used as a co-modifier. and / or platinum and / or copper and / or ruthenium and / or osmium and / or zirconium and / or palladium and / or vanadium and / or zinc, and alkenyl succinic acid derivatives with an average molecular weight of 500 up to 1200 Da, preferably from 600 to 900 Da.

The patent specification PL 216821 discloses a multifunctional additive with high thermal stability for light fuel oils containing from 5.0% (m / n) to 80.0% (m / m) of the active substance

PL 238 362 B1 with detergent and dispersant properties in the form of alkenyl succinimide-amides, a combustion modifier in the amount of 1.0% (m / m) to 70.0% (m / m) and / or an additive facilitating the ignition of light fuel oil , in an amount from 2.0% (m / m) to 50.0% (m / m) and / or a lubricity additive, in an amount from 5.0% (m / m) to 70.0% (m / m) ) and / or a wetting agent in an amount from 1.0% (m / m) to 70.0% (m / m) and / or a corrosion inhibitor in an amount from 1.0% (m / m) to 20.0 % (m / m) and / or oxidation inhibitor in the amount from 1.0% (m / m) to 50.0% (m / m) and / or demulsifiers and / or foam inhibitors, in an amount from 1.0 % (m / m) up to 30.0% (m / m) and / or a substance with biocidal properties, in an amount from 0.1% (m / m) to 30.0% (m / m) and / or tracer a fuel-soluble organic solvent in an amount of 0.1% (m / m) to 10.0% (m / m) and an organic solvent which is an oil fraction and / or contains oxygen. Synthetic saturated monocarboxylic acids with the number of carbon atoms in the alkyl chain from 6 to 12, preferably branched-chain, and / or their esters and / or amides and / or unsaturated fatty acids with the number of atoms are used as lubricating additive in the multifunctional additive according to patent PL 216821. carbon 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 of 200 to 600 Dalton and / or semiamides and / or amideesters of alkenyl succinic anhydrides and / or acids.

The main objective of the invention is to obtain a universal package of additives for heating oils, intended for the refining of heating oils, used in particular in highly energy-efficient central heating boilers, steam boilers, industrial furnaces and technological furnaces, which prevents adverse phenomena related to e.g. with the progressive oxidation processes occurring in the entire volume of the stored or stored fuel, resulting in the formation of deposits or delamination of the fuel, facilitates fuel atomization, improves the combustion process by limiting the amount of harmful substances emitted during the combustion process and prevents the accumulation of sediments and carbon deposits on the burner elements.

Surprisingly, it has been found that such properties are possessed by the universal fuel oil additive package according to the present invention, containing alkenyl succinimide-amides with a controlled content of imide and amide groups, a combustion modifier and an organic solvent.

SUMMARY OF THE INVENTION

A universal package of additives for fuel oils, according to the present invention, containing: I. reaction products of alkenyl succinic anhydride derivatives with amines, II. a combustion process modifier obtained by a method which includes the following steps:

1) a mixture of iron (III) and (II) compounds is co-precipitated from an aqueous solution of inorganic iron (III) salts and (II) salts using an alkali metal or ammonium hydroxide at a temperature of up to 90 ° C, precipitating in a solution at pH from 7 to 9, where:

- chlorides or sulphates or nitrates are used as inorganic iron (III) and (II) salts;

- the molar ratio of the inorganic iron (III) salt to the inorganic iron (II) salt is from 1.0: 0.3 to 1.0: 1.0;

- as the alkali metal hydroxide, aqueous solutions of sodium or potassium hydroxide are used;

the molar ratio of the inorganic iron (III) salt to the alkali metal or ammonium hydroxide is from 1.0: 3.0 to 1.0: 5.5;

2) a solution of an organic acid in a hydrocarbon solvent is introduced into the freshly precipitated mixture of iron (III) and (II) compounds obtained in step 1) and the resulting reaction mixture is heated to 110 ° C for 1 to 12 hours, while :

- the molar ratio of the inorganic iron (III) salt to the organic acid is from 2.0: 1.0 to 10.0: 1.0;

- as organic acids, dodecylbenzenesulfonic acid or dodecyltoluenesulfonic acid or didodecylbenzenesulfonic acid or naphthosulfonic acids with an average molecular weight from 250 to 400 Dalton or alkylbenzenesulfonic acid or alkyltoluenesulfonic acid with the number of carbon atoms in the alkyl chain from 24 to 35 or synthetic saturated monocarboxylic acids with the number of carbon atoms in the alkyl chain from 6 to 12, chain

Branched chain or saturated and unsaturated fatty acids with a number of carbon atoms in the alkyl chain from 10 to 24;

- aliphatic or aromatic hydrocarbon fractions with a boiling point from 90 ° C to 350 ° C and sulfur content up to 0.2% (m / m) are used as a hydrocarbon solvent;

3) after stage 2), the hydrocarbon phase containing iron (III) and (II) compounds is separated, and the iron compounds obtained in this way are conditioned and oxidized with air, oxygen or hydrogen peroxide at temperatures up to 110 ° C, obtaining:

- in the case of oxidation with oxygenated water - a water layer and a hydrocarbon layer containing iron (III) compounds, the water layer being separated from the hydrocarbon layer by decantation, after which the hydrocarbon layer is dried and cleaned, or in the case of oxidation with air or oxygen only the hydrocarbon layer containing iron (III) compounds, which is dried and purified;

III. organic solvent, being a petroleum fraction with a boiling point range from 180 to 220 ° C and containing more than 99% by mass of aromatic hydrocarbons, with a number of carbon atoms in the molecules mainly from 10 to 11, which does not contain polycyclic aromatic compounds, heavy metals and chlorinated hydrocarbons;

and optionally at least one ingredient selected from the group consisting of:

IV. a co-modifier of the combustion process, which is an organic complex compound or a salt of the following metals of the s-block or d-block of the periodic table: potassium, calcium, magnesium, strontium, manganese, cobalt, platinum, copper, ruthenium, osmium, zircon, palladium, vanadium, zinc, or a mixture of a complex compound and / or salt,

V. an additive preventing decomposition of the additive package, being a derivative of alkenyl succinic acid, with an average molecular weight from 500 to 1200 Da, being an ester, amide or imide, obtained by reacting alkenyl succinic anhydride with an alcohol or a primary or secondary amine with the number of carbon atoms in the alcohol molecule, or amines from 2 to 8, with an amount of hydroxyl groups in the alcohol from 1 to 2, and with an amount of amino groups in the amine from 1 to 4;

VI. lubricity additive, which is:

- saturated or unsaturated monocarboxylic or dicarboxylic acid with the number of carbon atoms in the alkyl chain from 6 to 24, straight or branched chain, or

- an ester of the abovementioned acid, being a reaction product of this acid or its anhydride with an aliphatic alcohol with the number of carbon atoms in the alcohol molecule from 3 to 9, or

- an amide of the abovementioned acid, being the reaction product of this acid or its anhydride, with an aliphatic amine with the number of carbon atoms in the amine molecule from 4 to 10;

The universal package of additives for heating oils is characterized by the fact that it contains, based on the total weight of the package:

I. from 3.0% (m / m) to 50.0% (m / m) of alkenyl succinimide-amides with a controlled content of imide and amide groups, acting as a detergent-dispersing and antioxidant-stabilizing additive, obtained by a method including the following steps:

A. a step of acylating a linear or branched polyalkylene polyamine with alkenyl succinic anhydride with a molecular weight of 750 to 2500 Daltons, the acylation step being carried out with a reagent ratio such that 1.0 to 3.0 mol of polyalkylene polyamine is present for 1.0 mole of polyalkylene polyamine moles of alkenyl succinic anhydride, the acylation reaction being carried out in a hydrocarbon solvent for 2 to 5 hours, in the temperature range from 80 to 95 ° C, under reduced pressure, under nitrogen or other gas atmosphere

Inert to oxalic acid or acetic acid or acetic anhydride as imidization catalyst, collecting reaction water;

B. the thermal conditioning stage of the post-reaction mixture obtained after the completion of stage A, which stage B is carried out in the temperature range from 50 to 130 ° C, in the presence of 0.5% (m / m) to 5% (m / m), based on the weight of the reaction mixture obtained after the completion of Step A, of an inorganic or organic compound containing at least one hydroxyl group, wherein said inorganic or organic compound containing at least one hydroxyl group is one compound selected from the groups a) to c) , or any mixture of them:

a) aqueous solutions of alkali metal hydroxides, alkaline earth metal hydroxides, amphoteric hydroxides

b) water;

c) linear or cyclic alcohols, monohydroxy or polyhydroxy alcohols with the number of carbon atoms in the molecule from 2 to 18 and the content of hydroxyl groups in the molecule from 1 to 4, whereby step B is carried out until the integration of proton signals in the 1HNMR spectrum, in the range 3 , 0-4.0 ppm derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, in relation to the integration of vinyl proton signals, in the range of 4.4-5.6 ppm (unit integration) , being from 2.0 to 3.5 and simultaneously maintaining the ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm, being from 1: 1.5 to 1: 3.5;

II. from 10.0% (m / m) to 70.0% (m / m) of the combustion process modifier;

III. from 10.0% (m / m) to 90.0% (m / m) of an organic solvent; and optionally at least one ingredient selected from:

IV. from 0.5% (m / m) to 10.0% (m / m) of the co-modifier of the combustion process;

V. from 0.5% (m / m) to 10.0% (m / m) of the additive preventing decomposition of the additive package;

VI. from 3.0% (m / m) to 60.0% (m / m) of the lubricating additive.

The term "inorganic or organic compound containing at least one hydroxyl group" as used herein means a chemical compound containing at least one hydroxyl group or an aqueous solution of a chemical compound containing at least one hydroxyl group.

For the purpose of the universal additive package of the present invention, alkenyl succinimide-amides with a controlled content of imide and amide groups are used, prepared by the method in which in step B, i.e. in the process of thermal conditioning of the post-reaction mixture obtained after the completion of step A, as an inorganic or organic compound containing at least one hydroxyl group is used:

a) aqueous solutions of alkali metal hydroxides, alkaline earth metal hydroxides, amphoteric hydroxides, in which the hydroxides are, for example: sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, zinc hydroxide, copper hydroxide;

b) water;

c) linear or cyclic alcohols, monohydroxy or polyhydroxy alcohols with the number of carbon atoms in the molecule from 2 to 18, and the content of hydroxyl groups in the molecule from 1 to 4, for example: n-propanol, n-butanol, n-pentanol, isopropanol, isobutanol, isopentanol, tert-butyl alcohol, tert-pentyl alcohol, sec-butyl alcohol, sec-pentyl alcohol, neopenatane alcohol, propane-1,2-diol, propane-1,3-diol.

Preferably, the universal package as component I contains alkenyl succinimide-amides with controlled content of imide and amide groups prepared by the method in which in step A the polyalkylene polyamine is diethylenetriamine or triethylene tetramine or tetraethylene pentaamine or pentaethylene hexaamine, or an alkene-anhydride mixture thereof, and an anhydride-anhydride mixture thereof is used as the polyalkylene polyamine. the reaction of ene polybutene and / or polyisobutene with maleic anhydride, the alkenyl succinic anhydride thus produced having a molar ratio of polybutene and / or polyisobutene to succinic anhydride of 1.0: 1.2, and

The highly reactive ene polybutene and / or polyisobutene for the preparation of alkenyl succinic anhydride is obtained by a method without the use of a chlorine-containing catalyst.

Preferably, the universal package as component I contains alkenyl succinimide-amides with a controlled content of imide and amide groups prepared by the method in which in step A, 1.0 to 1.2 moles of alkenylsuccinic anhydride per 1.0 mole of the polyalkylene polyamine corresponds, the acylation reaction is carried out in toluene for 3 to 4 hours, with a temperature range of 80-90 ° C, with a concentration of the imidization catalyst from 0.0075 to 0.015 moles per 1 mole of alkenyl succinic anhydride.

Preferably, the universal package as component I contains alkenyl succinimide-amides with controlled content of imide and amide groups, prepared by the method in which step B of thermal conditioning of the post-reaction mixture obtained after the completion of stage A is carried out at a temperature range of 70 to 100 ° C, in the presence of 1 5% (m / m) to 2.5% (m / m) of an inorganic or organic compound containing at least one hydroxyl group, whereby step B is carried out until the integration of proton signals in the ¹ HNMR spectrum, in the range of 3.0 -4.0 ppm derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, in relation to the integration of vinyl proton signals, in the range of 4.4-5.6 ppm (unit integration), of 2.5 to 3.0 and simultaneously maintaining the ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm, being from 1: 2.0 to 1: 2.5.

The universal additive package according to a preferred embodiment of the invention is characterized in that the combustion modifier contains from 5% (m / m) to 30% (m / m) iron based on the total weight of the modifier.

In the universal additive package of the present invention, known solvents are used as the organic solvent, for example: Shellsol A150® or Solvessol50®.

In the universal additive package of the present invention, known compounds are used as the organic complex compound as a co-modifier of the combustion process, for example: known compounds are used in the combustion process, for example: potassium oleate, calcium oleate, magnesium oleate, potassium sulfonate, calcium sulfonate, magnesium sulfonate.

The universal additive package according to a preferred embodiment of the invention is characterized in that the co-modifier of the combustion process contains from 5% (m / m) to 10% (m / m) of metals in the complex compound and / or salt based on the total weight of the co-modifier of the combustion process.

In the universal additive package of the present invention, known esters or amides or imides obtained by reaction of an alkenyl succinic acid anhydride, for example polyisobutylene succinic acid anhydride or tetrapropenyl succinic acid anhydride, with an alcohol, for example n-propanol, n-butanol, are used as an additive to prevent decomposition of the additive package in the present invention. , isopropanol, isobutanol or with a primary or secondary amine for example propylamine butylamine 2-methylpropylamine 2-methylbutylamine.

The known compounds are used as a lubricating additive in the universal additive package of the present invention:

- saturated or unsaturated monocarboxylic or dicarboxylic acid, for example: 4-methyldecanoic acid, 4-methylpentadecanoic acid, 4-methyl eicosanoic acid, 3-methyl-9-octadecaenoic acid, 3,7-dimethyl-6-octadecaenoic acid, heptanedioic acid, decanode, or

- an ester of the abovementioned acid, being the product of the reaction of said acid or its anhydride with an aliphatic alcohol, for example n-propanol, n-butanol, isopropanol, isobutanol, or

- an amide of the abovementioned acid, which is the product of the reaction of this acid or its anhydride with an aliphatic amine, for example with butylamine, pentylamine, 2-methylbutylamine, and 2-methylpentylamine.

The use of the universal additive package according to the invention for refining fuel oils reduces the amount of soot emitted, prevents the accumulation of coke deposits

On the burner elements and improves the stability of these types of fuels, which in turn prevents the inclusion of sludge on the bottom of the tanks, clogging of filters and installation lines.

The invention is explained in more detail in the following examples from 1 to 36, showing the composition of a fuel oil additive package intended for use, in particular, in highly energy-efficient central heating boilers, steam boilers, industrial furnaces and process furnaces, and the evaluation of selected performance properties of this additive package in test trials and position.

The use of the package with the composition according to the invention allows for the provision of fuel oil operating properties compliant with the requirements and prevents the occurrence of undesirable phenomena during the operation of this fuel. Known additives are used as components of the package, such as: a combustion process modifier, an organic solvent and possibly a co-modifier of the combustion process, an additive preventing decomposition of the additive package and a lubricating additive. When used in the amounts according to the invention, these additives offer the user a comprehensive solution to the various problems observed in the operation of fuel oils. The use of individual known additives in the package in the claimed concentration ranges guarantees that the user meets the above-mentioned requirements and at the same time does not adversely affect the antioxidant-stabilizing effect of alkenyl succinimide-amides with a controlled content of imide and amide groups. The examples show the composition and effects of the packages with an emphasis on illustrating the antioxidant-stabilizing effect of alkenyl succinimide-amides with controlled content of imide and amide groups, using exemplary substances at a selected dosage level as known additives.

However, these examples are not intended to limit the invention as they are illustrative only.

EXAMPLES

Example 1 - preparation of alkenyl succinimide-amides with a controlled content of imide and amide groups

59.5 g of alkenyl succinic anhydride under the trade name ERD751® (RE Specialty Chemicals), 10.4 g of tetraethylene pentamine with a boiling point of 190-240 ° C (at a pressure of 20 mbar), 30 cm ^{3 of} toluene and 0.1 g of oxalic acid. The reaction mixture was heated to 90 ° C and stirred for 3 hours under reduced pressure. The water evolving from the reaction was azeotroped away. The obtained reaction product, with an acid number of 0.89 mg KOH / g and a total base number of 119.42 mg KOH / g, contained about 70% (m / m) of alkenyl succinic acid imide with a characteristic band in the infrared spectrum resulting from the vibration of stretching bonds C = About the imide at 1703 cm ^-1 .

Hexyl alcohol was introduced into the reaction product obtained above in a weight ratio of the product to the alcohol of 40: 1. The mixture was homogenized by vigorous stirring in an ultrasonic bath. The mixture was thermally conditioned at 100 ° C. The process was monitored by registering spectra by 1HNMR spectroscopy. The process was completed after 24 hours, when the expected integration of signals in the range of 3.0-4.0 ppm, derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, was achieved, in relation to the integration of vinyl proton signals , of 2.51 and a ratio of the signal intensity at 3.60 ppm to the signal intensity at 3.30 ppm of 1: 2.1. The product, i.e. alkenyl succinimide amides with controlled imide and amide groups, was purified by distilling off the alcohol under reduced pressure. During the distillation, toluene was also distilled, the loss of which was supplemented with a fresh portion in order to obtain the appropriate viscosity of the product, resulting in easy handling.

Example 2 - preparation of alkenyl succinimide-amides with a controlled content of imide and amide groups

59.5 g of alkenyl succinic anhydride under the trade name ERD751® (RE Specialty Chemicals), 10.4 g of tetraethylene pentamine with a boiling point of 190-240 ° C (at a pressure of 20 mbar), 30 cm ^{3 of} toluene and 0.1 g of oxalic acid. The reaction mixture was heated to 90 ° C and stirred for 3 hours under reduced pressure. The water evolving from the reaction was azeotroped away. The obtained reaction product with an acid number of 0.89 mg KOH / g and a total base number of 119.42 mg KOH / g contained about 70% (m / m)

PL 238 362 B1 of alkenyl succinimide with a characteristic band in the infrared spectrum from the vibration of the C = O bonds of the imide stretching at 1703 cm ^-1 .

Demineralized water was introduced into the reaction product obtained above in a weight ratio of product to water of 40: 1. The mixture was homogenized by vigorous stirring in an ultrasonic bath. The mixture was thermally conditioned at 85 ° C. The process was monitored by registering spectra by 1HNMR spectroscopy. The process was completed after 48 hours, when the expected integration of signals in the range of 3.0-4.0 ppm from imide (CH2-N-imide) and amide (CH2-NH-amide) groups was achieved, compared to the integration of vinyl proton signals of 2.79 and the ratio of the signal intensity at 3.60 ppm to the signal intensity at 3.30 ppm of 1: 2.1. The product, ie alkenyl succinimide amides with controlled content of imide and amide groups, was purified by washing three times with distilled water and then distilling off the residual water under reduced pressure. During the distillation, toluene was also distilled, the loss of which was supplemented with a fresh portion in order to obtain the appropriate viscosity of the product, resulting in easy handling.

Example 3 - preparation of alkenyl succinimide-amides with a controlled content of imide and amide groups

59.5 g of alkenyl succinic anhydride under the trade name ERD751® (RE Specialty Chemicals), 10.4 g of tetraethylene pentamine with a boiling point of 190-240 ° C (at a pressure of 20 mbar), 30 cm ^{3 of} toluene and 0.1 g of oxalic acid. The reaction mixture was heated to 90 ° C and stirred for 3 hours under reduced pressure. The water evolving from the reaction was azeotroped away. The obtained reaction product, with an acid number of 0.89 mg KOH / g and a total base number of 119.42 mg KOH / g, contained about 70% (m / m) of alkenyl succinic acid imide with a characteristic band in the infrared spectrum resulting from the vibration of stretching bonds C = About the imide at 1703 cm ^-1 .

A 3% (m / m) aqueous sodium hydroxide solution was introduced into the above-obtained reaction product in a weight ratio of the product to sodium hydroxide solution of 65: 1. The mixture was homogenized by vigorous stirring in an ultrasonic bath. The mixture was thermally conditioned at 70 ° C. The process was monitored by recording spectra by ¹ HNMR spectroscopy. The process was completed after 52 hours, when the expected integration of signals in the range of 3.0-4.0 ppm from imide (CH2-N-imide) and amide (CH2-NH-amide) groups was achieved, compared to the integration of vinyl proton signals of 2.83 and the ratio of the signal intensity at 3.60 ppm to the signal intensity at 3.30 ppm of 1: 2.2. The product, ie alkenyl succinimide amides with controlled content of imide and amide groups, was purified by washing three times with distilled water and then distilling off the residual water under reduced pressure. During the distillation, toluene was also distilled, the loss of which was supplemented with a fresh portion in order to obtain the appropriate viscosity of the product, resulting in easy handling.

P r x l a d 4

Structure studies were carried out by 1HNMR spectroscopy for the products of Examples 1, 2 and 3. The spectra were recorded on a Bruker Avance III 600 MHz spectrometer, in solutions in chloroform-D6. The spectra processing included the Fourier transform FID (Free Induction Decay), manual spectral phasing, baseline correction using the Whittaker algorithm and calibration of the spectra for the residual solvent signal (due to the low content of TMS [tetramethylsilane] in used solvent), taking the position of the signal from chloroform-D6 in the 1HNMR spectra to be 7.26 ppm.

The analysis covered the integration of signals from imide (C H2-N-imide) and amide (CH2-NH-amide) groups (3.0-4.0 ppm) in relation to the integration of vinyl proton signals in the range of 4.4-5, 6 ppm (10 unit integration) and the ratio of the signal intensity at 3.60 ppm to the signal intensity at about 3.30 ppm. The results are included in Table 1.

PL 238 362 Β1

T a b I i c a 1

Results of signal integration analysis in ¹ HNMR spectra

A sample Integration of signals in the range of 3.0 - 4.0 ppm in relation to the integration of signals of vinyl protons in the range of 4.4 - 5.6 ppm Ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm The product of example 1 2.51 1: 2,1 The product of example 2 2.79 1: 2,1 The product of example 3 2.83 1: 2.2

Example 5 (comparative)

An alkenyl succinimide was prepared by the method of the invention covered by patent PL 147691 for the purpose of comparative studies.

1000 g of alkenyl succinic anhydride under the trade name ERD751® (RE Specialty Chemicals) was introduced into a glass reactor equipped with a mechanical stirrer, a condenser with an azeotrope and a heating mantle and heated to 90 ° C, a small stream of nitrogen was admitted and 49 g of tetraethylene pentaamine was dosed, then the temperature of the reaction mixture was increased to 120 ° C and 2 g of oxalic acid was added, the pressure in the reaction system was reduced to 53.2 kPa and the temperature was raised to 160 ° C and the temperature was maintained for 3.5 hours, the water that formed in the reaction was collected with a stream nitrogen. After completion of the reaction, 500 g of mineral oil having a viscosity of 10 mm 2 / s at a temperature of 100 ° C were added. The obtained reaction product contained 1.2% (m / m) of nitrogen.

Example 6 - production of the combustion process modifier

30 g of hydrated iron (II) sulphate and 45 g of hydrated iron (III) sulphate, 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 60 ° C, and after the temperature was established, 15% aqueous ammonia solution was added dropwise until the pH was 7.5. A mixture of 15.0 g of distilled olein with the trade name Oleina Radiacid 212, which is a mixture of saturated and unsaturated C16-C18 fatty acids in which the content of 9-octadecanoic acid is at least 70% (m / m) was added to the resulting suspension, 105.0 g of toluene and 90.0 g of the solvent Shellsol D60®. 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 resulting 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 a temperature of 60 ° C, and then 200.0 g of an aqueous solution of hydrogen peroxide with a concentration of 3.0% (w / w) 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. The combustion process modifier was obtained with the iron content equal to 12.7% (m / m) and the hydrodynamic diameter of the dispersed particles of iron compounds equal to 17.3 nm.

Example 7 - preparation of the co-modifier of the combustion process

4 g of potassium hydroxide previously ground in a mortar, 28 g of distilled olein with the trade name Oleina Radiacid 212, which is a mixture of saturated and unsaturated fatty acids C16-C18, was introduced into the reactor equipped with an anchor stirrer, heating system and a condenser with a Dean-Stark attachment. the content of 9-octadekaenoic acid is at least 70% (m / m), 5 g of water, 5 g of ethanol, 0.02 g of acetic acid and 100 g of xylene. It was heated under reflux until water evolution ceased. The solvents were evaporated in an evaporator. 30 g of potassium oleate, being a co-modifier of the combustion process, were obtained.

PL 238 362 B1

Example 8A

5 g of the product of Example 1, 4 g of the product of Example 6 and 21 g of the C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

Example 8B

To a reactor equipped with an anchor stirrer were introduced 7.5 g of the product of Example 1, 4 g of product from Example 6 and 18.5 g of aromatic hydrocarbon solvent, C9-C10 trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

Example 8C

To a reactor equipped with an anchor stirrer were introduced 10 g of the product of Example 1, 4 g of product from Example 6 and 16 g aromatic hydrocarbon solvent, C9-C10 trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

Example 9A

5 g of the product of example 2, 4 g of the product of example 6 and 21 g of a C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

Example 9B

To a reactor equipped with an anchor stirrer were introduced 7.5 g of product from Example 2, 4 g of product from Example 6 and 18.5 g of aromatic hydrocarbon solvent, C9-C10 trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

Example 9C

To a reactor equipped with an anchor stirrer were introduced 10 g of the product of Example 2, 4 g of product from Example 6 and 16 g aromatic hydrocarbon solvent, C9-C10 trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

Example 10A

5 g of the product from example 3, 12 g of iron 2-ethylhexanoate with an iron content of 6.1% (m / m) (manufacturer Alfa Aesar) and 21 g of the aromatic hydrocarbon solvent C9-C10 under the trade name were introduced into the reactor equipped with an anchor stirrer. Shellsol A150 ^® . The contents were stirred for 30 minutes at room temperature.

Example 10B

7.5 g of the product from example 3, 12 g of iron 2-ethylhexanoate with an iron content of 6.1% (m / m) (manufacturer Alfa Aesar) and 18.5 g of the aromatic hydrocarbon solvent C9- were introduced into the reactor equipped with an anchor stirrer. C10 with the trade name Shellsol A150 ^® . The contents were stirred for 30 minutes at room temperature.

Example 10C

10 g of the product from example 3, 12 g of iron 2-ethylhexanoate with an iron content of 6.1% (m / m) (manufacturer Alfa Aesar) and 16 g of the aromatic hydrocarbon solvent C9-C10 under the trade name were introduced into the reactor. Shellsol A150 ^® . The contents were stirred for 30 minutes at room temperature.

Example 11A

To a reactor equipped with an anchor stirrer, 5 g of the product of Example 5, 4 g of product from Example 6 and 21 g aromatic hydrocarbon solvent, C9-C10 trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

Example 11B

To a reactor equipped with an anchor stirrer were introduced 7.5 g of product from Example 5, 4 g of product from Example 6 and 18.5 g of aromatic hydrocarbon solvent, C9-C10 ester having the trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

Example 11C

To a reactor equipped with an anchor stirrer were introduced 10 g of the product of Example 5, 4 g of product from Example 6 and 16 g aromatic hydrocarbon solvent, C9-C10 trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

Example 12A

To a reactor equipped with an anchor stirrer, 5 g of the product of Example 1, 40 g of product from Example 6 and 30 g aromatic hydrocarbon solvent, C9-C10 trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

PL 238 362 B1

Example 12B

7.5 g of the product of example 1, 40 g of the product of example 6 and 27.5 g of a C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

Example 12C

10 g of the product of example 1, 40 g of the product of example 6 and 25 g of a C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

Example 13A

5 g of the product from example 2, 120 g of iron 2-ethylhexanoate with an iron content of 6.1% (m / m) (manufacturer Alfa Aesar) and 30 g of the aromatic hydrocarbon solvent C9-C10 with the trade name were introduced into the reactor equipped with an anchor stirrer. Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

Example 13B

7.5 g of the product from example 2, 120 g of iron 2-ethylhexanoate with an iron content of 6.1% (m / m) (manufacturer Alfa Aesar) and 27.5 g of the aromatic hydrocarbon solvent C9- were introduced into the reactor equipped with an anchor stirrer. C10 with the trade name Shellsol A150 ^® . The contents were stirred for 30 minutes at room temperature.

Example 13C

10 g of the product from example 2, 120 g of iron 2-ethylhexanoate with an iron content of 6.1% (m / m) (manufacturer Alfa Aesar) and 25 g of the aromatic hydrocarbon solvent C9-C10 with the trade name were introduced into the reactor equipped with an anchor stirrer. Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

Example 14A

5 g of the product of example 3, 40 g of the product of example 6 and 30 g of a C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

P r x l a d 14B

7.5 g of the product of example 3, 40 g of the product of example 6 and 27.5 g of a C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

Example 14C

10 g of the product of example 3, 40 g of the product of example 6 and 25 g of a C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

Example 15A

5 g of the product of example 5, 40 g of the product of example 6 and 30 g of a C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

Example 15B

7.5 g of the product of example 5, 40 g of the product of example 6 and 27.5 g of a C9-C10 aromatic hydrocarbon solvent under the trade name Shellsol A150® were introduced into a reactor equipped with an anchor stirrer. The contents were stirred for 30 minutes at room temperature.

Example 15C

To a reactor equipped with an anchor stirrer were introduced 10 g of product from Example 5, 40 g of product from Example 6 and 25 g aromatic hydrocarbon solvent, C9-C10 trade name Shellsol A150 ^®. The contents were stirred for 30 minutes at room temperature.

Example 16A

30 g of the product from Example 8A, 0.4 g of the product from Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (iNiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

PL 238 362 B1

Example 16B

30 g of the product from example 8B, 0.4 g of the product of example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (iNiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 16C

30 g of the product from Example 8C, 0.4 g of the product from Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 17A

30 g of the product of Example 9A, 0.4 g of the product of Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 17B

30 g of the product from Example 9B, 0.4 g of the product of Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 17C

30 g of the product from Example 9C, 0.4 g of the product of Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 18A

30 g of the product from Example 10A, 0.4 g of the product from Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 18B

30 g of the product from example 10B, 0.4 g of the product of example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 18C

30 g of the product from Example 10C, 0.4 g of the product of Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 19A

30 g of the product from Example 11A, 0.4 g of the product from Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

PL 238 362 B1

P r z k ł a d 19B

30 g of the product from example 11B, 0.4 g of the product of example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 19C

30 g of the product from Example 11C, 0.4 g of the product from Example 7, 0.4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB ) and 9.2 g of the lubricating additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.). The contents were stirred for 30 minutes at room temperature.

Example 20A

75 g of the product from Example 12A, 4 g of the product of Example 7, 4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

Example 20B

75 g of the product from example 12B, 4 g of the product of example 7, 4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

Example 20C

75 g of the product from Example 12C, 4 g of the product of Example 7, 4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

Example 21A

75 g of the product from Example 13A, 4 g of the product of Example 7, 4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150®. The contents were stirred for 30 minutes at room temperature

Example 21B

75 g of the product from Example 13B, 4 g of the product of Example 7, 4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

Example 21C

75 g of the product from Example 13C, 4 g of the product of Example 7 were introduced into the reactor equipped with an anchor stirrer, 4 g of the additive preventing decomposition of the additive package: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

PL 238 362 B1

Example 22A

75 g of the product from Example 14A, 4 g of the product of Example 7, 4 g of the additive preventing decomposition of the additive package were introduced into the reactor equipped with an anchor stirrer: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

Example 22B

To a reactor equipped with an anchor stirrer were introduced 75 g of the product of Example 14B, 4 g of product from Example 7 4 g of the additive to prevent the decomposition of the additive package: semiestru 2-propyl ester polyisobutylene trade name Koriten 100 ^® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150 ^® . The contents were stirred for 30 minutes at room temperature.

Example 22C

To a reactor equipped with an anchor stirrer were introduced 75 g of the product of Example 14C, 4 g of product from Example 7 4 g of the additive to prevent the decomposition of the additive package: semiestru 2-propyl ester polyisobutylene trade name Koriten 100 ^® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150 ^® . The contents were stirred for 30 minutes at room temperature.

Example 23A

To a reactor equipped with an anchor stirrer were introduced 75 g of the product of Example 15A, 4 g of product from Example 7 4 g of the additive to prevent the decomposition of the additive package: semiestru 2-propyl ester polyisobutylene trade name Koriten 100 ^® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150 ^® . The contents were stirred for 30 minutes at room temperature.

Example 23B

75 g of the product from Example 15B, 4 g of the product of Example 7 were introduced into the reactor equipped with an anchor stirrer, 4 g of the additive preventing decomposition of the additive package: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A ^® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150®. The contents were stirred for 30 minutes at room temperature.

Example 23C

75 g of the product from Example 15C, 4 g of the product of Example 7 were introduced into the reactor equipped with an anchor stirrer, 4 g of the additive preventing decomposition of the additive package: polyisobutylene succinic acid 2-propyl semester with the trade name Koriten 100® (INiG-PIB), 10 g lubricity additive: tall oil fatty acids under the trade name Hitec 4140A ^® (Candusa Corp.) and 7 g of aromatic hydrocarbon solvent C9-C10 under the trade name Shellsol A150 ^® . The contents were stirred for 30 minutes at room temperature.

P r z k ł a d 24

Test fuels containing the products of Examples 8-11 were prepared by incorporating them into light fuel oil in the amounts shown in Table 2. Light fuel oil has the properties shown in Table 3.

PL 238 362 Β1

Table 2

Composition of test fuels

Test fuel no Package from example Package dosage, mg / kg Fuel 1 8A 300 Fuel 2 8B 300 Fuel 3 8C 300 Fuel 4 9A 300 Fuel 5 9B 300 Fuel 6 90 300 Fuel 7 10A 300 Fuel 8 10B 300 Fuel 9 10C 300 Fuel 10 11A 300 Fuel 11 11B 300 Fuel 12 11C 300

Table 3

Properties of light fuel oil

Property Unit Findings Calorific value MJ / kg 45.6 Fractional composition to 250 ° C has distilled to 350 ° C has distilled % (V / V) % (V / V) 61.0 95.3 Density at 15 ° C kg / m3 826.7 Sulfur content mg / kg 50 Flash-point ° c 66 Oxidation resistance g / m3 3.1 Lubricity, corrected wear scar diameter (WS 1.4) at 60 ° C pm 566

Example 25

Test fuels containing the products of Examples 12-15 were prepared by incorporating them into the heavy fuel oil in the amounts shown in Table 4. The heavy fuel oil has the properties shown in Table 5.

Table 4

Composition of test fuels

Test fuel no Package from example Package dosage, mg / kg Fuel 13 12A 750 Fuel 14 12B 750 Fuel 15 12C 750 Fuel 16 13Λ 750 Fuel 1 7 13B 750 Fuel 18 13C 750 Fuel 19 14A 750 Fuel 20 14B 750 Fuel 21 14C 750 Fuel 22 15A 750 Fuel 23 15B 750 Fuel 24 15C 750

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Table 5

Properties of heavy fuel oil

Property Unit Findings Density at 15 ° C kg / m ³ 978, G Calorific value MJ / kg 40.8 Flash-point, ° C 99.0 Kinematic viscosity at 100 ° C mm ² / s 23.35 Pour point ° C +6 Sulfur content % {m / m) 0.43 Contaminant content % (jn / jn) 0.08 Water content % (m / ml less than 0.03 Ash residue % (m / m) 0.016 Coking residue % (mZm) 11.83 Vanadium content mg / kg 13.0 Flocculation coefficient 1.45 Stability by the stain method 4 Potential sediment content % (m / m) 0.82 Number of phase separation 14.0

Example 26

Test fuels containing the products of Examples 16-19 were prepared by incorporating them into light fuel oil in the amounts shown in Table 6. Light fuel oil has the properties shown in Table 3.

Table 6 Composition of test fuels

Test fuel no Package from example Package dosage, mg / kg Fuel 25 IGA 400 2G fuel 16B 400 Fuel 27 16C 400 Fuel 28 17A 400 Fuel 29 17B 400 Fuel 30 17C 400 Fuel 31 18A 400 Fuel 32 18B 400 Fuel 33 18C 400 Fuel 34 19Λ 400 Fuel 35 19B 400 Fuel 36 19C 400

Example 27

Test fuels containing the products of Examples 20-23 were prepared by incorporating them into the heavy fuel oil in the amounts shown in Table 7. The heavy fuel oil has the properties shown in Table 5.

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Table 7 Composition of test fuels

Test fuel no Package from example Package dosage, mg / kg Fuel 37 20A 1000 Fuel 38 20B 1000 Fuel 39 20C 1000 Fuel 40 21A 1000 Fuel 41 2 IB 1000 Fuel 42 21C 1000 Fuel 43 22A 1000 Fuel 44 22B 1000 Fuel 45 22C 1000 Fuel 40 23A 1000 Fuel 47 23B 1000 Fuel 48 23C 1000

Example 28

Refined light fuel oils - test fuels from 1 to 12 and from 25 to 36 and light fuel oil with properties from Table 3 were tested for oxidative stability according to PN-EN 16091 "Liquid petroleum products - middle distillates, fatty acid methyl esters (FAMA) and mixtures of these - Determination of oxidative stability in the small-scale accelerated oxidation test ”. The test consisted in measuring the pressure changes in a tightly closed test vessel, into which 5 ml of the tested sample were introduced, and then oxygen to obtain a pressure of 700 kPa ± 5 kPa (at ambient temperature). The pressure vessel with the sample was heated to a temperature of 140 ° C. The pressure in the vessel was recorded in Is intervals until reaching the end point, i.e. a pressure drop of 10% from its highest value. The result of the test was the time that elapsed from the beginning of the test, i.e. from the moment the sample reaches the temperature of 140 ° C until the pressure inside the test vessel drops by 10%. The test results are presented in Table 8.

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Table 8

Results of studies on oxidative stability of light fuel oil

Test fuel Test result according to ΡΝΈΝ 16091, min Change in relation to the fuel with the properties in table 3,% Fuel with properties from table 3 69 - Fuel 1 81 +17.4 Fuel 2 84 +21.8 Fuel 3 88 +27.5 Fuel 4 79 +14.5 Fuel 5 83 +20.3 Fuel 6 87 +26.1 Fuel 7 84 +21.7 Fuel 8 87 +26.1 Fuel 9 92 +33.3 Fuel 10 69 0 Fuel 11 68 1.4 Fuel 12 67 2.9 Fuel 25 77 +11.6 Fuel 26 80 +15.9 Fuel 27 84 +21.7 Fuel 28 79 +14.5 Fuel 29 85 +23.2 Fuel 30 88 +27.5 Fuel 31 80 +15.9 Fuel 32 83 +20.3 Fuel 33 89 +29.0 Fuel 34 70 +1.4 Fuel 35 69 0 Fuel 36 69 0

The packages obtained according to the present invention, containing alkenyl succinimide-amides with a controlled content of imide and amide groups, improve the oxidation stability of the fuel (test according to PN-EN 16091) to about 33%, while the packages containing the acylation products of polyalkylene polyamines with alkenyl succinic anhydride, obtained by the method according to the invention covered by the patent PL 147691 improve this parameter by a maximum of 1.4%.

Example 29

Refined light fuel oils - test fuels 25, 28, 31 and 34 and light fuel oil with properties from Table 3 were placed in transparent glass bottles and exposed to sunlight at room temperature. After 2 months, aging fuel oxidation resistance was tested according to the EN-ISO 12205 method. The test results are presented in Table 9.

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Table 9

The results of the test of resistance to oxidation of light fuel oils

Test fuel Oxidation resistance according to EN-ISO 12205, g / m ³ Light fuel oil with the properties in Table 3, against aging 3.1 Light fuel oil with properties from Table 3, after aging 173.0 Fuel 25 3.0 Fuel 28 4.1 Fuel 31 3.8 Fuel 34 167.4

Example 30

Heavy fuel oil with properties from Table 5 and heavy fuel oils - fuels from 13 to 24 and from 37 to 48 were placed in glass bottles in a dryer at 80 ° C. A glass tip connected to a technical air source was placed at a distance of about 0.5 cm from the bottom of the bottles. The flow-meter-controlled air flow was set at 30 dcm ³ / hr. (or 60 dcm ³ / hour). Aeration in high temperature conditions was carried out for 1 week, after which the oil samples were homogenized and subjected to the filtration time test at 100 ° C through a GF / A filter, at a pressure of 40 kPa. The filtration time was assumed from the dosing of the sample until the appearance of a "dry" filter was obtained. The weight of the sample subjected to filtration was about 10 g. For comparison purposes, the filtration time was given in terms of 1 g of the sample. The test results are presented in Table 10.

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Table 10

Results of filtration time of aged samples of heavy fuel oil

Test fuel Air flow, dm ³ / h Filtration time after aging calculated per Ig of filtered fuel, s The difference of filtration time in relation to the fuel with properties from table 3,% Heavy fuel oil with properties from table 3 thirty 68.8 60 233.7 Fuel 13 thirty 67.8 1.45 60 224.5 3.94 Fuel 14 thirty 66.1 3.92 60 221.0 5.43 Fuel 15 thirty 68.5 0.44 60 230.0 1.58 Fuel 16 thirty 65.4 4.94 60 221.5 5.22 Fuel 17 thirty 66.0 4.07 60 222.8 -4.66 Fuel 18 thirty 64.8 -5.81 60 220.9 5.48 Fuel 19 thirty 66.1 3.92 60 224.3 -4.02 Fuel 20 thirty 66.2 3.78 60 225.4 3.55 Fuel 21 thirty 65.3 5.09 60 221.8 5.09 Fuel 22 thirty 68.9 0.15 60 234.0 0.13 Fuel 23 thirty 68.8 0 60 233.8 0.04 Fuel 24 thirty 69.0 0.29 60 233.4 0.13 Fuel 37 thirty 67.1 2.47 60 222.0 5.01 Fuel 38 thirty 68.0 -1.16 60 221.3 5.31 Fuel 39 thirty 66.1 -3.92 60 225.3 3.59 Fuel 40 thirty 65.2 5.23 60 226.7 3.00 Fuel 41 thirty 66.4 -3.49 60 222.8 4.66 Fuel 42 thirty 67.0 -2.62 60 225.0 -3.72 Fuel 43 thirty 65.0 5.52 60 221.0 5.43 Fuel 44 thirty 65.4 -4.94 60 221.1 5.39 Fuel 45 thirty 67.2 -2.33 60 224.7 -3.85 Fuel 46 thirty 69.1 0.44 60 233.6 0.04 Fuel 47 thirty 68.9 0.15 60 234.4 0.30 Fuel 48 thirty 69.0 0.29 60 233.9 0.09

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The packages obtained according to the present invention, containing alkenyl succinimide amides with a controlled content of imide and amide groups, reduce the filtration time of aged heavy fuel oils in the range from about 0.5% to about 6%, while the packages containing the acylation products of polyalkylene polyamines with alkenyl succinic anhydride, obtained by the method of the invention covered by patent PL 147691, improve this parameter by no more than 0.3%.

Example 31

Heavy fuel oils - fuels 37, 40, 43, 46 and heavy fuel oil with properties from Table 5 were aged at 80 ° C for 1 month. After this time, tests were carried out to assess the stability of these fuels. The test results are presented in Table 11.

Table 11

Results of testing the stability of heavy fuel oils after the aging process

Property Sediment content,% (jn / ni) The degree of purity Number of phase separation Heavy fuel oil with properties from table 3 0.82 4 14.0 Fuel 37 0.40 3 0.5 Fuel 40 0.48 3 1.5 Fuel 43 0.44 3 L6 Fuel 46 0.8 4 14.0

In fuel enriched with packages obtained according to the present invention, containing alkenyl succinimide-amides with a controlled content of imide and amide groups, the content of sediments after the aging period was about 2 times lower than in the base fuel oil and in the fuel oil containing acylation products of polyalkylene polyamines with alkenyl succinic anhydride. according to the invention covered by patent PL 147691. The number of phase separation qualifies the aged base fuel and the fuel containing acylation products of polyalkylene polyamines with alkenyl succinic anhydride, obtained by the method of the invention covered by patent PL 147691, to the group of unstable fuels, while fuels enriched with packages obtained according to the present invention containing alkenylsuccinimides with a controlled content of imide and amide groups to the group of stable fuels. An improvement in the purity level of heavy fuel oils enriched with the packages obtained according to the present invention, containing alkenyl succinimide-amides with controlled content of imide and amide groups by 1 degree compared to the base fuel, was also observed.

Example 32

For enriched light fuel oils-test fuels 26, 29, 32 and 35, and for light fuel oil with properties from Table 3, the equilibrium interfacial tension was determined by the plate method. For this purpose, the voltage between the refined fuel phase and the demineralized water as a function of time was determined. After reaching the thermodynamic equilibrium of the system, the thermodynamic voltage was read. The interfacial tension characterizes the surfactant properties and, by definition, the lower the interfacial tension, the better the substance is estimated to have better surfactant properties, and hence - dispersing properties. The results of the determined interfacial tensions are presented in Table 12.

Table 12

Results of research on the interfacial tension of light fuel oils

Test fuel Interfacial tension, mN / m Light fuel oil with properties from Table 3 21.09 Fuel 26 0.86 Fuel 29 0.34 Fuel 32 0.54 Fuel 35 0.48

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Example 33

Refined light fuel oils - test fuels 25, 28, 31 and 34 and light fuel oil with properties from Table 3 were tested for the propensity to contaminate fuel atomizers, according to the CEC F-05-93 method, in the Peugeot XUD9 engine. After completion of the test, a stream of air was passed through the fuel atomizers and on this basis the decrease in their patency was measured. According to the World Fuel Charter, the criterion qualifying diesel oil for use is obtaining a test result of the nozzle patency reduction index at a needle lift of 0.10 mm, not higher than 85%. The results of the conducted tests are presented in Table 13.

Table 13

Results of the study of the tendency of light fuel oils to contaminate fuel atomizers

Test fuel Tendency to contamination of nozzles according to CEC F-05-93: The index of reducing the patency of nozzles at the needle lift 0.10 mm in [%] Light fuel oil with properties from Table 3 81.0 Fuel 25 30.0 Fuel 28 28.0 Fuel 31 24.2 Fuel 34 26.4

Example 34

Refined light fuel oils - test fuels 25, 28, 31 and 34 and light fuel oil with properties from Table 3 were burnt in a Paromat Triplex high-pressure steam boiler with a rated power of 80 kW by Viessmann, equipped with a burner with a nozzle operating at a pressure of 2000 kPa. The emission of gaseous pollutants and combustion efficiency were tested. The GA-40 exhaust gas analyzer from Eljack Electronics was used to measure the concentration of exhaust gas components. Determination of the concentration of hydrocarbons in the exhaust gas was carried out by gas chromatography in accordance with the PN-89 / Z-040014 standard. The results of the exhaust gas emission tests are presented in Table 14.

Table 14

Results of research on emissions from light fuel oil combustion carried out in a high-pressure steam boiler

Test fuel Combustion efficiency,% CO emission, mg / Nm ³ NO _x emission, mg / Nm ³ Light fuel oil with properties from Table 3 around 90 19 86 Fuel 25 around 94 5 86 Fuel 28 about 96 9 89 Fuel 31 around 95 7 86 Fuel 34 around 95 8 87

Example 35

Heavy fuel oils - fuels 37, 40, 43, 46 and heavy fuel oil with properties from Table 5 were tested for the impact on elastomers according to the PN-ISO 1817/01 method, using a sample of the material of gaskets used in fuel installations in power plants. The test assessed the change in volume and hardness of the seal material after contacting the fuels from Examples 18 and 19 and - comparatively - with the base fuel under strictly defined conditions. The test results are presented in Table 15.

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Table 15

The results of the research on the influence of heavy fuel oil on elastomers

Test fuel Volume change after 168 h (temp. 80 ° C),% Volume change after 336 h (temp. 80 ° C),% Hardness change after 168 h (temperature 80 ° C), IRHD Hardness change after 336 h (temperature 80 ° C), IRHD Heavy fuel oil with properties from Table 5 6.7 7.2 1.7 0.9 Fuel 37 6.7 7.6 1.6 0.8 Fuel 40 7.0 7.6 2.1 1.3 Fuel 43 6.8 7.5 2.0 1.4 Fuel 46 6.8 7.6 '1.7 i, i

Example 36

Operational tests were carried out for heavy fuel oils - fuels 37 and 40 in a heat and power plant on a boiler equipped with oil kindling burners arranged in pairs in two rows, on the rear and front walls. Two-factor low-pressure K-type gas-dynamic burners with a wide range of thermal regulation (30 4-120%), fed with heavy fuel oil, with a capacity of up to 1000 kg / h, were used for the tests. The effectiveness of the additive packages was monitored by visually observing the burner flame and the smoke from the chimney. The test results are presented in Table 16.

Table 16

Results of operational tests carried out in the CHP plant

Property Fuel 37 Fuel 40 Duration of the test, min 8 16 19 18 Package dosing, multiplicity xl x2 xl x2 Visual assessment of the smoke from the chimney a lot of haze, dark smoke little smoke, bright smoke little smoke, bright smoke little smoke, bright smoke Visual inspection of the burner flame dark, smoky, bright, shining bright, shining bright, shining Effectiveness short tall tall tall

INDUSTRIAL APPLICABILITY

In the above examples it has been proved that the universal fuel oil additive package according to the present invention is suitable for industrial use.

Claims (7)

Patent claims 1) a mixture of iron (III) and (II) compounds is co-precipitated from an aqueous solution of inorganic iron (III) salts and (II) salts using an alkali metal or ammonium hydroxide at a temperature of up to 90 ° C, precipitating in a solution at pH from 7 to 9, where: - chlorides or sulphates or nitrates are used as inorganic iron (III) and (II) salts; PL 238 362 B1 - the molar ratio of the inorganic iron (III) salt to the inorganic iron (II) salt is from 1.0: 0.3 to 1.0: 1.0; - as the alkali metal hydroxide, aqueous solutions of sodium or potassium hydroxide are used; - the molar ratio of the inorganic iron (III) salt to the alkali metal or ammonium hydroxide is from 1.0: 3.0 to 1.0: 5.5; 1. Universal package of additives for fuel oils containing: I. reaction products of alkenyl succinic anhydride derivatives with amines; II. a combustion process modifier obtained by a method which includes the following steps: 2. Universal package according to claim The method of claim 1, characterized in that it comprises I. from 5.0% (m / m) to 40.0% (m / m) of alkenyl succinimide-amides with a controlled content of imide and amide groups; II. from 12.0% (m / m) to 55.0% (m / m) of the combustion process modifier; III. from 20.0% (m / m) to 55.0% (m / m) of an organic solvent; and optionally at least one ingredient selected from: IV. from 1.0% (m / m) to 5.0% (m / m) of the co-modifier of the combustion process; V. from 1.0% (m / m) to 5.0% (m / m) of the additive preventing decomposition of the additive package; VI. from 5.0% (m / m) to 45.0% (m / m) of the lubricating additive. PL 238 362 B1 2) a solution of an organic acid in a hydrocarbon solvent is introduced into the freshly precipitated mixture of iron (III) and (II) compounds obtained in step 1) and the resulting reaction mixture is heated to 110 ° C for 1 to 12 hours, while : - the molar ratio of the inorganic iron (III) salt to the organic acid is from 2.0: 1.0 to 10.0: 1.0; - as organic acids, dodecylbenzenesulfonic acid or dodecyltoluenesulfonic acid or didodecylbenzenesulfonic acid or naphthosulfonic acids with an average molecular weight from 250 to 400 Dalton or alkylbenzenesulfonic acid or alkyltoluenesulfonic acid with the number of carbon atoms in the alkyl chain from 24 to 35 or synthetic saturated monocarboxylic acids with the number of carbon atoms in the alkyl chain from 6 to 12, branched-chain or saturated and unsaturated fatty acids with the number of carbon atoms in the alkyl chain from 10 to 24; - aliphatic or aromatic hydrocarbon fractions with a boiling point from 90 ° C to 350 ° C and sulfur content up to 0.2% (m / m) are used as a hydrocarbon solvent; 3. Universal package according to claim A process according to claim 1, characterized in that component I comprises alkenylsuccinimide-amides with a controlled content of imide and amide groups, prepared by the process in which in step A the polyalkylene polyamine is diethylenetriamine or triethylene tetraamine or tetraethylene pentaamine or pentaethylene hexaamine, or an anhydride mixture thereof, and alkenyl hexa-amide as an anhydride mixture thereof, and an anhydride which is a product of the reaction of ene polybutene and / or polyisobutenes with maleic anhydride, the alkenyl succinic anhydride so produced having a molar ratio of polybutene and / or polyisobutene to succinic anhydride of 1.0: 1.2, and used for the preparation of alkenyl succinic anhydride highly reactive ene polybutene and / or polyisobutene, obtained by a method without the use of a chlorine-containing catalyst. 3) after stage 2), the hydrocarbon phase containing iron (III) and (II) compounds is separated and the iron compounds obtained in this way are conditioned and oxidized with air, oxygen or hydrogen peroxide at temperatures up to 110 ° C, obtaining: - in the case of oxidation with water, an oxidized water layer and a hydrocarbon layer containing iron (III) compounds, the water layer being separated from the hydrocarbon layer by decantation and the hydrocarbon layer being dried and cleaned, or - in the case of oxidation with air or with oxygen, only the hydrocarbon layer containing iron (III) compounds, which is dried and cleaned; III. organic solvent, being a petroleum fraction with a boiling point range from 180 to 220 ° C and containing more than 99% (m / m) of aromatic hydrocarbons with the number of carbon atoms in the molecules mainly from 10 to 11, which does not contain polycyclic aromatic compounds, heavy metals and chlorinated hydrocarbons; and optionally at least one ingredient selected from the group consisting of: IV. a co-modifier of the combustion process, which is an organic complex compound or a salt of the following metals of the s-block or d-block of the periodic table: potassium, calcium, magnesium, strontium, manganese, cobalt, platinum, copper, ruthenium, osmium, zircon, palladium, vanadium, zinc, or a mixture of a complex compound and / or salt; V. additive preventing decomposition of the additive package, being a derivative of alkenyl succinic acid, with an average molecular weight from 500 to 1200 Da, being an ester, amide or imide, obtained by reacting alkenyl succinic anhydride with an alcohol or a primary or secondary amine with the number of carbon atoms in the alcohol molecule or amines from 2 to 8, with an amount of hydroxyl groups in the alcohol of from 1 to 2 and an amount of amino groups in the amine from 1 to 4; VI. lubricity additive, which is: - saturated or unsaturated monocarboxylic or dicarboxylic acid with the number of carbon atoms in the alkyl chain from 6 to 24, straight or branched chain, or - an ester of the abovementioned acid, which is a reaction product of this acid or its anhydride with an aliphatic alcohol with the number of carbon atoms in the alcohol molecule from 3 to 9, PL 238 362 B1 or - an amide of the abovementioned acid, being a reaction product of this acid or its anhydride with an aliphatic amine having the number of carbon atoms in the amine molecule from 4 to 10; characterized in that it contains, based on the total weight of the packet: I. from 3.0% (m / m) to 50.0% (m / m), alkenyl succinimide-amides with a controlled content of imide and amide groups, acting as a detergent-dispersant and antioxidant-stabilizing additive, obtained by a method including the following steps : A. a step of acylating a linear or branched polyalkylene polyamine with alkenyl succinic anhydride with a molecular weight of 750 to 2500 Daltons, the acylation step being carried out with a reagent ratio such that 1.0 to 3.0 mol of polyalkylene polyamine per 1.0 mole of polyalkylene polyamine is moles of alkenyl succinic anhydride, the acylation reaction being carried out in a hydrocarbon solvent for 2 to 5 hours, at a temperature of 80 to 95 ° C, under reduced pressure, under nitrogen or other inert gas, in the presence of oxalic acid or acetic acid or acetic anhydride as imidization catalyst, receiving reaction water; B. the step of thermal conditioning of the post-reaction mixture obtained after the completion of stage A, which stage B is carried out in the temperature range from 50 to 130 ° C, in the presence of 0.5% (m / m) to 5% (m / m), based on the weight of the reaction mixture obtained after completion of Step A, of an inorganic or organic compound containing at least one hydroxyl group, wherein said inorganic or organic compound containing at least one hydroxyl group is one compound selected from the groups a) to c ), or any mixture of them: (a) aqueous solutions of alkali metal hydroxides, alkaline earth metal hydroxides, amphoteric hydroxides; b) water; c) linear or cyclic alcohols, monohydroxy or polyhydroxy alcohols with the number of carbon atoms in the molecule from 2 to 18 and the content of hydroxyl groups in the molecule from 1 to 4, whereby step B is carried out until the integration of proton signals in the 1HNMR spectrum, in the range 3 , 0-4.0 ppm derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, in relation to the integration of vinyl proton signals, in the range of 4.4-5.6 ppm (unit integration) , being from 2.0 to 3.5 and simultaneously maintaining the ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm, being from 1: 1.5 to 1: 3.5; II. from 10.0% (m / m) to 70.0% (m / n) of the combustion process modifier; III. from 10.0% (m / m) to 90.0% (m / m) of an organic solvent; and optionally at least one ingredient selected from: IV. from 0.5% (m / m) to 10.0% (m / m) of the co-modifier of the combustion process; V. from 0.5% (m / m) to 10.0% (m / m) of the additive preventing decomposition of the additive package; VI. from 3.0% (m / m) to 60.0% (m / m) of the lubricating additive. 4. Universal package according to claim The process according to claim 1, characterized in that component I contains alkenylsuccinimide-amides with a controlled content of imide and amide groups, prepared by the method in which in step A, 1.0 to 1.2 mol of alkenylsuccinic anhydride corresponds to 1.0 mol of the polyalkylene polyamine, the acylation reaction is carried out by in toluene for 3 to 4 hours, in the temperature range from 80-90 ° C, with the concentration of the imidization catalyst from 0.0075 to 0.015 mol per 1 mol of alkenyl succinic anhydride. 5. Universal package according to claim A process according to claim 1, characterized in that component I comprises alkenyl succinimide-amides with a controlled content of imide and amide groups, prepared by the method in which step B of the thermal conditioning of the post-reaction mixture obtained after the completion of step A is carried out in the temperature range from 70 to 100 ° C in the presence of 1.5% (m / m) to 2.5% (m / m) of an inorganic or organic compound containing at least one hydroxyl group, whereby step B is carried out until the integration of proton signals in the 1HNMR spectrum, in the range 3.0-4.0 ppm derived from imide (CH2-N-imide) and amide (CH2-NH-amide) groups, in relation to the integration of vinyl proton signals, in the range of 4.4-5.6 ppm (unit integration ) of 2.5 to 3.0 while maintaining the ratio of the signal intensity at about 3.60 ppm to the signal intensity at about 3.30 ppm, being from 1: 2.0 to 1: 2.5. 6. Universal package according to claim The method of claim 1, wherein the combustion modifier comprises 5% (m / m) to 30% (m / m) iron, based on the total weight of the modifier. 7. Universal package according to claim The process of claim 1, wherein the combustion co-modifier comprises 5% (m / m) to 10% (m / m) of metals in the complex compound and / or salt based on the total weight of the combustion co-modifier.