SE530604C2 - Fuel or crude oil additive and fuel or crude oil composition including said additive - Google Patents

Description

539 604 heavy deposits with polluting metals. Barium, which is known to reduce the development of smoke, forms toxic salts. Cerium is less effective due to its high molecular weight.

Ferrocene, Fe (C5H5) p_, is probably the best known and most studied organometallic additive.

It is known as a soot inhibitor in combustion and has been used for many years. A problem that often occurs with Ferrocene is that it tends to deposit oxide on the walls of the combustion chamber, which can have serious degrading long-term effects.

There are well-known known proposals for additives in the field of technology, which are intended to counteract the described disadvantages. FR-A-2 172 797 thus describes basic iron salts of organic acids and FR-A-2 632 966 describes a mixture of iron hydroxide AND a basic calcium soap as an aid in improving the combustion of heavy fuel oil. US-A-4,129,539 strongly recommends basic and oil-soluble magnesium salts of sulfonic acids as an oil additive.

EP-A-475 196 discloses a mixture essentially comprising at least one oil-soluble carbanyl compound of manganese and at least one oil-soluble neutral or basic salt of an alkali metal or alkaline earth metal and an organic acid as an oil additive.

It has been quite surprising that individual or combinations of iron formates are, in terms of improved combustion and their effects, particularly effective additives in fuel and / or crude oil. The present invention thus relates to a fuel or crude oil additive comprising at least one iron (III) and / or iron (II) formate in an amount of between 0.5 and 99.5% by weight of said oil additive, and at least one within prior art known dispersant, stabilizer and / or other auxiliary additive.

Embodiments of said fuel and / or crude oil additive may additionally comprise at least one carboxylate, mineral salt, oxide or hydroxide of calcium, such as calcium formate and / or calcium sulfonate in a weight ratio Fe to Ca of, for example, between 0.5-99.5 and 99, 5-0.5% by weight calculated as metal, and / or at least one organic or inorganic metal compound, carboxylate, mineral salt, oxide and / or hydroxide other than those mentioned (III) and / or iron (II) fonnate and other than said calcium carboxylate or mineral salt, such as iron (II) fumarate.

Preferred organic or inorganic additional compounds include those containing iron, cerium, barium, beryllium, calcium, magnesium, copper, silver, zinc, cadmium, titanium, zirconium, molybdenum, chromium, tungsten, cobalt, nickel, lanthanum and / or ytterbium as active metal. Particularly preferred are carboxylates, mineral salts, oxides and hydroxides of barium, beryllium, calcium, magnesium, copper, zinc, zirconium, molybdenum, iron, nickel, cerium and yttrium.

Further embodiments of said fuel or crude oil additive comprise fl surfactant additives comprising an active amount of at least one dispersant and / or stabilizer for asphaltenes in a content of, for example, between 0.1 and 50% by weight based on said carboxylates 530 B04 and / or fl surfactant additives comprising an active amount of at least one anionic, cationic and / or nonionic surfactant in a content of 1-10, such as 2-5,% by weight of said additive.

Additional embodiments of the fuel and / or crude oil additive of the present invention include dry powders or granules comprising an active amount of at least one anti-baking agent, such as a magnesium and / or calcium salt of an oxidized microwax, a phenolic resin, a fatty acid derivative, an amide and / or an amide wax.

A surfactant additive of the present invention, including aqueous ones comprising one or more anionic, cationic and / or nonionic surfactants, is prepared by mixing together the individual components, as specified, with or without the use of solvents or dispersants, such as a hydrocarbon solvent / oil and / or a glycol. Suitable solvents include rapeseed oil methyl ester and other biodegradable solvents and suitable dispersants include pine fatty acid adducts. Preparation of said composition is suitably carried out at atmospheric pressure and at a temperature of, for example, 15-10 ° C, preferably 20-70 ° C.

A powdered fuel and / or crude oil additive according to the present invention is preferably prepared by first grinding the constituent metal compounds to a particle size of preferably less than 100 μm, using a suitable grinding equipment. Although it is possible to mix the metal compounds and process aids, such as anti-baking agents from the group consisting of, for example, a magnesium and / or calcium salt of an oxidized microwax, a phenolic resin, a fatty acid derivative, an arnide and / or an amide wax, for desired composition in e.g. a belt mixer, the components are preferably ground individually before mixing in, for example, a mixer or conical powder mixer.

Suitable embodiments of the additive according to the present invention include, for example, formulations with i) Fe (II) - and / or Fe (III) formate as the only active compound and used in a dry dosage of between 0.5 and 200 ppm, preferably approx. 50 ppm, based on the fuel and / or crude oil, ii) Fe (II) and / or Fe (II) fonnate and Ca-carboxylate or mineral salt, such as Ca-fonnate or Ca-sulfonate, as active metal compounds in a weight ratio of between 0.5 and 99.5% and vice versa, such as Fe 30% by weight and Ca 70% by weight or Fe 70% by weight and Ca 30% by weight, iii) Fe (II) and / or Fe (II) formate and Mg carboxylate, mineral salt, oxide or preferably hydroxide, as active metal compounds in a weight ratio between 0.5 and 99.5% and vice versa, such as Fe 5% by weight and Mg 95% by weight for boilers and Fe 50% by weight 530 5011 and Mg 50% by weight for marine and land-based diesel applications, with a preferred dosage of 1 part by weight of additive per 3000 parts by weight of fuel and / or crude oil, preferably 1 part by weight of additive per 500-2000 parts by weight of fuel oil and / or crude oil, iv) Fe (H) and / or Fe (III) formate, Mg carboxylate, mineral salt, oxide or preferably hydroxide and Ca carboxylate or mineral salt as active m ethyl compounds in relative quantities F e to Mg according to (i) and (ii) above and a Ca amount of between 0.5 and 99.5% by weight * 1 / O, such as Fe 20% by weight, Mg 50% by weight and Ca 30% by weight for the treatment of deposits in boilers and Fe 25% by weight, Mg 5% by weight and Ca 70% by weight for reducing particulate emissions, in dosages according to (i) and (ii) above, v) Fe (II) and / or Fe (III), Mg and Ca according to (i) - (iv) and in addition Ce and / or Mn carboxylate, mineral salt, oxide or hydroxide, and vi) formulations according to (i) - (v) above with, for example, a dispersant / stabilizer for asphaltenes, in a content of between 0.1 and 50% by weight based on the formulation.

Said formulations are based on constituent active metal combinations. The dry content of surface compositions is limited only by the dispersion system adapted to practical viscosity, which makes dosing pumps work efficiently. Formulations with low metal contents are often more useful in marine and land-based diesel engines, taking into account the type of dosing pump and the effective dosing amount, as well as the importance of the additive being distributed in the fuel. The present invention does not prevent the addition of additional metal compounds as mentioned above and / or the complete or partial replacement of said carboxylates with other metal salts, which may or may not be overbased.

The present invention relates in a further aspect to a fuel or crude oil composition comprising a fuel and / or crude oil and at least one additive as above in an amount of, for example, between 0.5 and 5000 ppm, such as 0.5-500, 50 -200, 2-2000 or 100-1000 ppm.

Said brim and / or crude oil composition is in particularly preferred embodiments a brim oil composition for boilers or is a marine fuel oil a.

The present invention relates in a further aspect to the use of a bristle and / or crude oil additive as above and to the use of an iron (H1) or iron (H) formate to obtain improved combustion properties, such as reduced smoke and / or particulate emissions. and / or reduced soot formation, in fuel or crude oil compositions, especially in boiler compositions and in marine fuel compositions.

The additive according to the present invention and the fuel and / or crude oil composition comprising said additive have particularly desirable properties and also synergistic effect with special grain component combinations, such as iron and calcium and iron, cerium and magnesium.

Furthermore, the use of iron (III) or iron formate according to the present invention is a very effective combustion promoter. It ensures complete combustion while reducing soot formation. In addition, great environmental benefits are obtained with reduced emissions of flue gas particles and it is also possible to obtain biodegradable additives. Additives including, for example, cerium and magnesium can reduce deposits and corrosion in the combustion unit.

The present invention differs from known use of combinations of metal compounds as combustion additives / combustion enhancers in that overbased metal salts are not used, although combinations comprising overbased metal salts may be allowed. Instead, so-called inorganic metal salts and combinations of inorganic metal salts and inorganic metal salts are used. The combustion additive / combustion enhancer can be made more efficient by using said solvents, dispersant and / or stabilizers, which gives a more complete combustion and stability of heavy oils.

It is understood that those skilled in the art without further explanation, using the description above, may take full advantage of the present invention. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the foregoing description. In the following exemplary embodiments, fuel oil compositions comprising an additive are shown, according to the present invention, which compositions are thermogravimetric and calorimetric analyzed and compared with oil compositions without additive and oil compositions comprising iron (II) fumarate and F errocene, respectively. The results are reported in diagrams 1-3.

Execution and comparison examples Balance from TA instruments, model SDT 2960, was used for thermogravimetric tests.

The instrument simultaneously performs DSC and TGA analyzes and its temperature range was between 25 ° C and 1500 ° C, with a heating gradient of between 100 ° C / min and 100 ° C / min. Heliurene, argon, nitrogen, air and acid can act as a fuel chain atmosphere.

Used fuel oil complied with the Venezuelan fuel oil specification and was supplied by Roman Laguna Power Plant, Maracaibo, Venezuela.

The following additives and additive amounts were evaluated: Sample 1: 200 ppm iron (II) formate.

Sample 2: 200 ppm iron (III) formate.

Sample 3: 200 ppm iron (II) foriniate + 200 ppm calcium formate.

Sample 4: 200 ppm iron (II) fumarate + 200 ppm calcium forlïliaï- Sample 5 (comparison y 200 ppm iron (II) fumarate. 530 B04 Sample 6 (comparison) 200 ppm Ferrocene.

Control: O-sample without additive.

The test procedure was the same for all samples and the ternary analysis sequence was: - Light materials were first stripped with nitrogen until the sample reached 400 ° C.

The recovery gradient was 10 ° C / min and the rate of nitrogen fl was 60 ml / min.

- When the sample reached 400 ° C, air was injected into the combustion chamber at the same fl velocity rate, 60 ml / min. The heating gradient was the same as with the above nitrogen reduction.

- The samples were kept in the incinerator at 700 ° C.

- Mass reduction, heat dissipation and peak temperature were measured with DSC and noted.

- The test was repeated twice and the average for each evaluation partner was calculated.

The results are reported in the attached diagrams 1-3 and can be summarized: iron (II) - and iron (IIl) form the highest mass reduction at 4-500 ° C. Iron (II) formate in combination with calcium shows the highest mass reduction at 5-600 ° C. Calcium in combination with iron (II) - or iron (III) form1ate increases the mass reduction at lower temperatures. Iron (11) - or iron (III) formate in combination with calcium results in increased heat dissipation, which generates the highest amount of energy.

Claims (22)

530 E04 1. PATENT REQUIREMENTS Fuel or crude oil additive comprising at least one metal carboxylate and at least one solvent, dispersant, stabilizer, anti-emollient and / or other adjuvant known in the art, characterized in that said at least one metal carboxylate is an iron (III) or iron (II) formate and that said formate is present in the additive in an amount of between 0.5 and 99.5% by weight. A fuel or crude oil additive according to claim 1, wherein said additive further comprises at least one carboxylate or mineral salt of calcium. Fuel or crude oil additive according to claim 2, characterized in that said carboxylate or mineral salt of calcium is calcium formate or calcium sulfonate. Fuel or crude oil additive according to Claim 2 or 3, a weight-ratio Fe to Ca of between 0.5-99.5 and 99.5-0.5% by weight, calculated as metal. Fuel or crude oil additive according to any one of claims 1-4, characterized in that said additive further comprises at least one organic or inorganic metal compound other than said iron (HI) or iron (II) formate OCh fi lmaï other than said carboxylate or mineral salt of calcium. Fuel or crude oil additive according to claim 5, characterized in that said further at least one organic or inorganic metal compound is a carboxylate, mineral salt, oxide or hydroxide. Fuel or crude oil additive according to claim 5 or 6, characterized in that said further at least one organic or inorganic metal purifier is from the group consisting of carboxylates, mineral salts, oxides and hydroxides of iron, cerium, calcium, magnesium, copper, Silver, Zinc, cadmium, titanium, zirconium, molybdenum, chromium, tungsten, cobalt, nickel, lanthanum, ytterbiurn, barium or beryllium. Fuel or crude oil additive according to any one of claims 1-7, characterized in that said additive further comprises iron (II) fumarate. 10. 11. 12. 13. 14. 15. 16. 17. 18. 530 B04 nä F? Fuel or crude oil additive according to any one of claims 1-8, characterized in that said additive is a surfactant composition comprising an active amount of at least one solvent, dispersant and / or stabilizer. Fuel or crude oil additive according to claim 9, characterized in that said solvent, dispersant and / or stabilizer is a dispersant for asphaltenes, which is present in an amount of between 0.1 and 50% by weight based on said carboxylates. Fuel or crude oil additive according to any one of claims 1-10, characterized in that said additive is a surfactant composition comprising an active amount of at least one anionic, cationic and / or nonionic surfactant. Fuel or crude oil additive according to claim 11, characterized in that said surfactant is present in an amount of between 1 and 10, such as 2-5,% by weight based on said additive. Fuel or crude oil additive according to any one of claims 1-12, characterized in that said additive is a surfactant composition comprising at least one hydrocarbon solvent or process oil. Fuel or crude oil additive according to any one of claims 1-13, characterized in that said additive is a surfactant composition comprising rapeseed oil methyl ester. Fuel or crude oil additive according to: any one of claims 1-8, characterized in that said additive is a dry powder or dry granules comprising an active amount of at least one anti-baking agent. Fuel or crude oil additive according to claim 15, characterized in that said anti-baking agent is a magnesium and / or calcium salt of an oxidized micro-wax, a phenolic resin, a fatty acid derivative, an amide and / or an amide wax. Fuel or crude oil composition characterized in that it comprises at least one fuel and / or crude oil and an active amount of at least one additive according to any one of claims 1-16 or an active amount of at least one iron (III) or iron (II ) forrniat. Fuel or crude oil composition according to claim 17, characterized in that said additive is present in an amount of between 0.5 and 19. 20. 21. 22. 530 EO4 5000 ppm, such as between 0.5 and 500 ppm or between 50 and 200 ppm, based on said fuel and / or crude oil. Fuel or crude oil composition according to claim 17 or 18, characterized in that said fuel and / or crude oil composition is a fuel oil composition or a marine fuel composition. Use of a fuel and / or crude oil additive according to any one of claims 1-16 in a fuel and / or crude oil composition. Use of iron (III) and / or iron (II) formate as an additive in a fuel and / or crude oil composition. Use according to claim 20 or 21, wherein said fuel and / or crude oil composition is a fuel oil composition or a marine fuel composition.