FR2979633A1 - COMPOSITION OF BURNING KEROSENE LIQUID FUEL ADDITIVES AND USES THEREOF - Google Patents

Abstract

The present invention relates to additive compositions that improve the burning qualities of liquid fuel type Burning Kerosene or Burning Oil or kerosene or heating oil in which they are incorporated. These liquid fuels thus additives are suitable as fuels for heating appliances, or in fixed appliances for producing energy, or in appliances for supplying the energy necessary for cooking food, to any type of heating system. heating: domestic boilers (spray burner), spray boilers, in particular those operating with a bag burner, and more particularly the cooking and / or heating appliances, stoves, AGA® boilers or Rayburn® boilers.

Description

TECHNICAL FIELD The present invention relates to a high quality fuel consisting of a Burning Kerosene or Burning Oil type liquid fuel or kerosene fuel oil or a domestic fuel oil additives. This high quality fuel can be used for energy production, heating or cooking for family or collective use.

Burning Kerosene type fuels (BUK) are liquid fuels with distillation temperatures between those of gasoline and those of diesel and properties rather similar to those of diesel fuel. They are very present on the Anglo Saxon market. Two categories of BUK are available on this market: - BUK class C2 according to the British standard BS 2869 (BUK C2 or Kerosene Regular) which is a standard kerosene intended for conventional heating installations - BUK class Cl according to the English standard BS 2869 (BUK Cl or Prermium Oil), which is a deflavored BUK C2, has characteristics similar to those of an aviation fuel. BUK Cl or C2 type liquid fuels or lamp oils can be used in heating appliances, or in stationary energy-producing appliances, or in appliances for supplying the energy necessary for cooking food. . These fuels are suitable for any type of heating system: domestic boilers (equipped with a spray burner), spray boilers, especially those operating with a sleeve burner (continuous burner), such as cooking and / or heating appliances , stoves, AGA® or Rayburn® boilers. By way of example of fuels, mention may be made of the liquid fuel of the BUK C2 type marketed by the applicant under the name Ketrul® as well as the liquid fuel marketed by the applicant under the name Kerdane® which has properties equivalent to those of BUK Cl or aviation kerosene. 110902-Text of deposit EN State of the art. In some combustion appliances such as spray stoves or ranges and / or hand-operated burner boilers, the liquid fuel passes through a small diameter feed pipe, usually metal, to reach the combustion chamber. . The walls of this duct closest to the combustion chamber are subjected to very high temperatures for residence times which can be significant, more particularly for appliances where the fuel flow is low. This greatly increases the risk of thermal degradation of the fuel and can lead to the formation of solid deposits on the walls of the conduit, resulting in a reduction in the diameter available for the passage of the fuel and a possible reduction of the flow, or an interruption of the supply of the combustion chamber. Then, in some heaters or cooking, the fuel reaches a combustion pot in which it stays at high temperature (250 ° C to 380 ° C), a few minutes to 1 hour before being vaporized and burned. Under such conditions thermal cracking can occur which results in the formation of solid deposits which lead to degradation of the combustion.

To avoid too much degradation of the quality of combustion over time, the manufacturers of these devices recommend maintenance of the combustion system every 6 months. In some cases, more frequent maintenance is required even before 6 months of use. To solve these problems and increase the time interval between two maintenances, EP 2 147 966 has proposed a liquid fuel additive composition which comprises a) at least one phenol or phenol / amine antioxidant, phenol / amine preference, b) at least one metal passivator, c) at least one metal sequestrant such as N, N'-disalicylidene 1,2-diaminopropane, especially a copper sequestrant, d) at least one an anti-corrosion agent. These additive compositions, although having, under certain conditions of use, very good performances making it possible to maintain the quality of combustion, may in certain cases be subjected to thermal cracking at high temperature, which inhibits the efficiency. of the additive and causes a potential clogging of the feed circuit of the sleeve burner or and / or the burn pot by the formation of residues during thermal cracking. DESCRIPTION OF THE INVENTION The present invention provides a liquid fuel additive with an additive composition having excellent combustion properties and which avoids the problems mentioned above. The liquid fuel additive according to the invention can be used in particular as fuel for thermal appliances and in particular for appliances where the fuel flow is low; the problems of plugging the supply ducts from the fuel storage tank to the combustion chamber are avoided but also the fuel ensures excellent combustion quality while limiting solid deposits at the burner, i.e. unburned. This has the effect of significantly increasing the time interval between two maintenances. A first object relates to a higher quality liquid fuel BUK, kerosene or domestic fuel oil, adapted to energy production devices and / or heating and / or for cooking food. This high quality fuel has improved properties over a standard fuel. For the purposes of the present invention, several properties of the fuel are improved, in particular the oxidation stability, the quality of the combustion, and possibly the odor. Can also be improved: the cold resistance, the corrosion resistance ... The invention also provides a liquid fuel additive composition BUK type or kerosene and / or domestic fuel comprising the following components: a) at least one hindered phenol type antioxidant (al kyl phenol), b) at least one metal sequestrant, in particular copper, or chelating agent, and preferably 110902-DE deposit text c) at least one perfuming agent and / or odor masking and / or reodorant, and / or d) at least one marker or tracer additive. The compositions according to the invention may also contain one or more additives as follows: e) at least one biocidal additive, f) one or more additives improving the cold-holding properties: cloud point, filterability limit temperature (TLF), point flow and / or anti-sedimentation, g) at least one lubricant additive, h) at least one anti-corrosion additive. Depending on the nature and miscibility of additives a) and b), c) and / or d) possibly present, but also any other additives, such as those defined below from e) to h), the additive composition according to the invention may also contain a hydrocarbon organic solvent and optionally a cosolvent or compatibilizing agent which may be chosen from organic solvents, especially those derived from petroleum fractions. Preferably, the additive composition according to the invention comprises at least one hydrocarbon organic solvent and / or at least one compatibilizing or co-solvent agent. The antioxidant (s) a) may contain or consist of at least one compound comprising at least one hindered phenol group (mono- or polysubstituted phenol); as an example of hindered phenol type antioxidants, mention may be made of 2,6-di-tert-butyl-4-methylphenol (BHT) (CAS No. 128-37-0), the tert- butyl hydroquinone (TBHQ) (CAS No. 1948-33-0), 2,6-di-tert-butyl phenol (CAS No. 128-39-2) and 2,4 di-tert-butyl phenol (CAS N 96-76-4), 2,4-dimethyl-tert-butyl phenol CAS No. 1879-09-0), pyrogallol (CAS No. 87-66-1), tocopherol (CAS No. 7616-22-0), 4,4'-methylene bis (2,6-di-tert-butyl phenol) (CAS No. 118-82-1), alone or in admixture. The metal sequestrant (s) b) may be chosen from amines substituted with N, N'-disalicylidene groups, such as N, N'-disalicylidene 1,2-diaminopropane (CAS No. 94-91-7) 110902 DETAILED DESCRIPTION OF THE INVENTION The one or more scenting and / or odor masking agents and / or deodorants c), preferably present in the additive compositions according to the invention, may be chosen for example from: organic tricyclics described in EP 1,591,514 which are organic tricyclic compounds as well as aliphatic or aromatic aldehydes such as vanillin, aliphatic or aromatic esters, such as benzyl acetate, alcohols, such as terpene alcohols such as linalool 3,7-dimethyl-1,6-octadiene-3-ol), or else phenylethyl alcohols, ketones, such as crystalline camphor, maltol or ethylmaltol, essential oils , such as oils try those derived from citrus fruits, alone or in mixtures. Advantageously, a mixture of at least one organic tricyclic compound and at least one aldehyde, an ester, a hydroxide, a ketone, an oil, is preferably used as perfume, odor masking or reodorant c). essential as defined above. The optional marker (s) d), preferably present in the additive compositions according to the invention, may especially be chosen from the following aliphatic or cycloaliphatic esters: embedded image 3a, 4,5,6,7,7a 4-hexahydro-4,7-methano-1H-inden-5 (or 6) -yl-isobutyrate (CAS No. 67634-20-2), tricyclodecenyl propionate (CAS No. 17511-60-3) 3 hexenyl (CAS No. 3681-71-8), ethyl linalool (CAS No. 10339-55-6), prenyl acetate (CAS No. 1191-16-8), ethyl myristate (CAS No. 06-1) tert-butyl cyclohexyl acetate (CAS No. 32210-23-4) butyl acetate (CAS No. 123-86-4), 4,7-methano-1h-inden-6- ol, 3a, 4,5,6,7,7a-hexahydro-, acetate (CAS No. 5413-60-5) ^ ethyl caprate (CAS No. 110-38-3) 110902-Depository Text Preferred additive compositions according to the invention comprise: from 2 to 50, preferably from 5 to 30, parts by weight of hindered phenol type antioxidant (s) or mono or polysubstituted phenol a), from 2 to 20, preferably from 2 to 10, parts by weight of metal sequestrant (s) b), from 3 to 20, preferably from 5 to 15, parts by weight of scenting agent (s) and / or masking agent (s) and / or odorant (s) c), from 0 to 15 parts by weight of tracer (s) d), from 20 to 70 parts by weight of organic solvent (s) hydrocarbon (s). In addition to the above components, the preferred compositions may also contain: from 0 to 20, preferably from 5 to 15, parts by weight of organic co-solvent (s) or compatibilizing agent (s) from 0 to 30 parts by weight of other additives, such as, for example, additives e) to h). The additive compositions according to the invention have the additional advantage of being storage stable for at least several months at room temperature (-15 to +40 ° C.) and can therefore be stored in a deposit before mixing with the fuel. Burning Kerosene type or kerosene. A second object of the invention relates to a method for preparing the additive compositions as defined above, by mixing, preferably at room temperature, in one or more steps according to any suitable mixing means: components or additives a) and b), as described above, and preferably also components c) and / or d), as described above, and optionally one or more of the components e) to h) as described above, and / or one or more other additives, - a hydrocarbon organic solvent an organic co-solvent. The liquid fuel according to the invention of higher combustion quality may be prepared by mixing in one or more stages, generally at room temperature, liquid fuel, additive composition or compositions according to the invention. the invention (additives a) and b), and preferably additives c) and / or d), optionally the solvent (s) and / or co-solvent (s), and any other possible additives, such as additives e) to h).

It would not be departing from the scope of the invention by mixing the liquid fuel, the components of the composition or compositions of the invention one by one. A third subject of the invention relates to a liquid fuel composition comprising: a major part comprising a liquid fuel which is a mixture of liquid hydrocarbons having distillation temperatures of between 180 and 370 ° C., preferably between 180 and 280 ° C. ° C and more particularly between 180 and 260 ° C. These mixtures are generally derived from cuts of the middle distillate type, from refineries and / or agrofuels and / or biofuels and / or biomass and / or synthetic fuels, and in particular kerosene cuts; these cuts from petroleum refineries generally contain a few percent of aromatic compounds and can be used as liquid fuels or can be subjected to dearomatization, in particular by hydrogenation, having the effect of very strongly reducing the concentration of aromatic compounds (typically less than or equal to at 2% by volume); deflavored mixtures having better combustion properties than mixtures with higher aromatic content; the liquid fuels may also have a composition close to that of the middle distillates of diesel or domestic fuel type. a minor portion comprising at least one additive composition as defined above, and optionally one or more other additives not forming part of the additive composition or compositions according to the invention. The liquid fuel composition according to the invention preferably comprises from 50 to 3000 ppm by weight, preferably from 150 to 3000 ppm by weight of additive composition (s) as defined. above, and preferably from 250 to 1,500 ppm m / m.

A fourth object of the invention relates to the use of liquid fuel compositions as defined above as fuels for the production of energy, for heating and / or for cooking. The high quality liquid fuel according to the invention, ie additive with at least one additive composition according to the invention can advantageously be used as a fuel for certain types of thermal apparatus and in particular for apparatus where the fuel flow is low. Preferably, the additives e) to h) additive compositions according to the invention, such as additives a) to d), are not sensitive to thermal cracking which occurs under the combustion conditions of the thermal appliances and cooking appliances, and in particular for thermal cracking which occurs under the combustion conditions of heating and / or cooking appliances of the types equipped with a bag burner (for example stoves and / or boilers of AGA® or Rayburn® type) Example 1 Preparation of additive compositions An additive composition called composition A according to the invention is prepared by mixing at room temperature the following components: 8 parts by weight of a commercial mixture of anti-oxidants of the type hindered phenols a) (comprising as a major component of 2,6-di-tert-butyl phenol (CAS No 129-39-2): 30-60% by weight of 2,4,6-tri-tert-butylphenol (CAS No 732 -26-3): 5-10, 2-tert-butyl-ph Enol (CAS # 88-18-6): 0.1-5%; 2,4-di-tert-butyl phenol (CAS No 96-76-4): 0.01-0.1%), - 3 parts by weight of N, N'-disalicylidene 1,2-diaminopropane (CAS No. 94-91-7) (metal sequestering agent b), 6 parts by weight of re-oxidizing agent c), 10 parts by weight of 2-ethyl hexanol (compatibilizing agent), the complement to 100 parts by weight of weight of Solvarex 10 (heavy aromatic organic solvent) marketed by the applicant. By way of comparison, an additive composition according to the teaching of EP 2 147 966 and designated Composition B is prepared according to the following procedure: At room temperature, 15 parts by weight of phenol antioxidants are mixed together. amine, 7 parts by weight passivator of benzotriazole type copper, 3 parts by weight of anti-corrosion (mixture of oleic acid, linoleic and linolenic acid dimer esters), 6 parts by weight of resorbing agent 10 parts by weight of 2-ethyl hexanol (compatibilizing agent) - the complement to 100 parts by weight of Solvarex 10 (heavy aromatic organic solvent) marketed by the applicant.

Thermal Stability The thermal stability of the additive compositions according to the invention was evaluated using standard methods JFTOT® (Jet Fuel Thermal Oxidation Tester) and Conradson Carbon.

Thermal stability - JFTOT® measured according to ASTM D3241 modified standard (350 ° C test temperature instead of 260 ° C) Thermal stability measurements are carried out according to the JFTOT® test (Jet Fuel Thermal Oxidation Test) according to the modified ASTM D3241 standard (Test temperature of 350 ° C. instead of 260 ° C.) on different samples of Burning Kerosene type (BUK) liquid fuel with or without additive to the additive composition according to the invention A or with the comparative composition B. The test is hardened by working with a treatment rate equivalent to 5 times the nominal dose called here "d" (with d = 500 ppm m / m).

The results are summarized in Table 1 below. Table 1 Test no. Delta liquid fuel P Tube dimension 110902-Deposit text FR (in mm Hg) (ASTM) 419 Blank BUK 1> 4 420 BUK + 5 * d Composition B 1> 4 421 BUK + 5 * d composition A 1 1 These results show that at a temperature representative of that of the burn pot or the fuel supply pipe upstream of the burn pot (typically 350 ° C.), the liquid fuel additive with composition A according to FIG. The invention forms much less deposits than that additivated with composition B. Burning quality - measurement of Conradson Carbon according to the modified NF-T60-116 standard (test temperature 350 ° C. instead of 550 ° C.) This standardized test has was adapted to the temperature conditions encountered in the burner before combustion, ie the tests were carried out at 350 ° C instead of 550 ° C. This test involves burning the volatile effluents as they form while pyrolyzing the residue under a non-inert atmosphere; the residue is weighed. The result of the test corresponds to the mass proportion of residue obtained relative to the initial mass of burned fuel. The test is hardened by working with a treatment rate equivalent to 5 times the nominal dose called here "d" (here = 500 ppm m / m).

Table 2 shows the results of the modified Conradson Carbone test at 350 ° C. 110902-Deposit text FR Table 2 Sample% of residue vs initial mass BUK + 5 * d of composition B 0.09 BUK + 5 * d of composition A 0.04 The difference observed between the results obtained on the liquid fuel additive with the composition A according to the invention and that additive with the comparative composition B is significant: the amount of residue obtained for the first product is much lower than for the second. When the BUK fuel is additive with the composition A, it forms much less solid residues at 350 OC than in the presence of the composition B. 110902-Deposit Text EN

Claims (12)

REVENDICATIONS1. Burning Kerosene type liquid fuel additive compositions or kerosene or domestic fuel oil comprising a) at least one hindered phenol-type antioxidant (mono- or polysubstituted), b) at least one metal sequestrant, in particular copper, and preferably c) at least one scent and / or odor-masking and / or re-odorant, and / or d) at least one marker or tracer. 2. Compositions according to claim 1 further containing at least one hydrocarbon organic solvent, and optionally at least one co-solvent or compatibilizing agent, and optionally other additives. 15 3. Compositions according to claim 1 or 2, comprising one or more additives: e) at least one biocidal additive, f) one or more additives improving the cold-holding properties, g) at least one lubricant additive, 20 h ) at least one anticorrosive additive. 4. Compositions according to one of claims 1 to 3, comprising a) at least one antioxidant chosen from molecules containing at least one phenol group, such as di-tert-butyl-2,6-methyl-4-phenol (BHT), tert-butyl hydroquinone (TBHQ), 2,6 or 2,4 di-tert-butyl phenol, 2,4-dimethyl-6-tert-butyl phenol, pyrogallol, tocopherol, 4,4'-methylene bis (2,6-di-tert-butyl phenol), alone or as a mixture; b) at least one metal sequestrant selected from compounds having at least one N, N'-disalicylidene group, such as N, N'-disalicylidene 1,2-diaminopropane; And preferably c) at least one scent and / or odor-masking and / or re-odorant, preferably selected from the organic tricyclic compounds described in EP 1.591.514 as well as aliphatic or aromatic aldehydes such as vanillin, aliphatic or aromatic esters, such as benzyl acetate, Alcohols, such as linalool, phenylethyl alcohols, ketones, such as crystallized camphor, ethylmaltol, essential oils, such as the essential oil derived from citrus fruits, and mixtures thereof, and advantageously the mixture of at least one organic tricyclic compound and at least one aldehyde, an ester, an alcohol, a ketone, an essential oil; and / or d) at least one tracer or label, preferably chosen from the following aliphatic or cycloaliphatic esters: 3a, 4,5,6,7,7a-hexahydro-4,7-methano-1h-inden-5 (or 6) -yl isobutyrate - tricyclodecenyl propionate - cis 3 hexenyl acetate - ethyl linalool - prenyl acetate - ethyl myristate - para tertiary butyl cyclohexyl acetate - butyl acetate - 4,7-methano-1h-inden-6- ol, 3a, 4,5,6,7,7a-hexahydro-, acetate-ethyl caprate; and optionally at least one solvent and / or one co-solvent and / or one or more other additives. 5. Compositions according to any one of claims 1 to 4 comprising: from 2 to 50, preferably from 5 to 30, parts by weight of hindered phenol type anti-oxidant agent (s) or mono phenol or polysubstituted a), from 2 to 20, preferably from 2 to 10, parts by weight of sequestrant (s) of metals (b), and preferably from 5 to 15, parts by weight of perfume agent (s) and / or odor masking (s) and / or odorant (s) c), from 0 to 15 parts by weight of tracer (s) d), from 20 to 70 parts by weight of organic solvent (s) hydrocarbon (s). Compositions according to claim 5 further comprising from 0 to 20, preferably from 5 to 15, parts by weight of organic co-solvent (s) or compatibilizing agent (s), 30 parts by weight of other additives, such as for example additives e) to h). 7. Process for the preparation of a composition as defined in any one of claims 1 to 6, by mixing, preferably at room temperature, components of said composition in one or more steps. A liquid fuel composition comprising a major part of a liquid hydrocarbon mixture of Burning Kerosene type or kerosene or domestic oil having distillation temperatures between 180 and 370 ° C, preferably between 180 and 280 ° C. ° C and particularly between 180 ° C and 260 ° C, an aromatic content of up to 20%, preferably less than or equal to 1%, said mixture based on liquid hydrocarbons comprising cuts of distillates middle types , from refineries and / or agrofuels and / or biofuels and / or biomass and / or synthetic fuels; a minor portion of at least one additive composition as defined in any one of Claims 1 to 6. 9. Composition according to claim 8 comprising from 50 to 3,000 ppm, preferably from 250 to 1,500 ppm m / m of at least one additive composition as defined in any one of claims 1 to 6. Use of a liquid fuel composition as defined in claim 8 or 9 as fuel for energy production, for heating and / or for cooking, and especially for cooking and / or heating in burner apparatus with handles 110902-Depository Text EN 11. Use of a composition according to claim 8 or 9 as fuel for heating apparatus, boilers and spray stoves. 12. Use of a composition according to claim 8 or 9 as fuel stoves equipped with sleeve burner. 110902-Deposit Text FR