WO2009090760A1 - Fuel additives - Google Patents
Fuel additives Download PDFInfo
- Publication number
- WO2009090760A1 WO2009090760A1 PCT/JP2008/052949 JP2008052949W WO2009090760A1 WO 2009090760 A1 WO2009090760 A1 WO 2009090760A1 JP 2008052949 W JP2008052949 W JP 2008052949W WO 2009090760 A1 WO2009090760 A1 WO 2009090760A1
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- WO
- WIPO (PCT)
- Prior art keywords
- ferrocene
- lecithin
- fuel
- fuel additive
- oil
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
Definitions
- the present invention relates to a fuel additive containing ferrocene and / or a ferrocene derivative, and more particularly, a fuel containing a ferrocene and / or ferrocene derivative enhanced by the addition of lecithin to promote combustion, dust reduction, NOX reduction, and the like. It relates to additives.
- Patent Document 1 discloses that in the presence of a fuel additive composition comprising ferrocene and a derivative thereof and an aromatic solvent, an aliphatic solvent, and / or a petroleum solvent that is a liquid organic carrier for dissolving the ferrocene.
- a fuel additive composition comprising ferrocene and a derivative thereof and an aromatic solvent, an aliphatic solvent, and / or a petroleum solvent that is a liquid organic carrier for dissolving the ferrocene.
- Patent Document 2 discloses that as a conditioning method for a diesel engine, carbon-containing deposits in the combustion chamber are removed by adding 20 to 30 ppm of ferrocene to the fuel, and fuel consumption per driving distance is about 5%. It has been shown to decrease.
- Patent Document 3 discloses an engine in which 1 to 100 ppm of ferrocene and its derivatives are directly added to a fuel as an additive to a fuel oil for an internal combustion engine composed of heavy residual oil, without blending other additive substances. And methods for reducing carbonaceous deposits on its accessories.
- the ferrocene and ferrocene derivatives used in these inventions have the disadvantage that their solubility in aromatic solvents, aliphatic solvents and petroleum solvents is very low.
- Ferrocene is generally in a solid state. In particular, it takes considerable stirring power and time to dissolve solid ferrocene, depending on the size of the solid. Even if a small amount is added, it does not dissolve easily, and if it does not dissolve in advance before it is added to the fuel, problems will occur in the internal combustion engine. Therefore, it is currently dissolved in a solvent in a dissolution tank with a stirrer and then added to the fuel. It is.
- the present invention has been made in view of such problems of the prior art, and an object of the present invention is to provide a fuel in which the contained ferrocene and / or ferrocene derivative can be easily and stably dissolved in the fuel. It is to provide an additive.
- the present inventors have found that the above object can be achieved by using ferrocene and / or a ferrocene derivative together with lecithin, and have completed the present invention. It was.
- the fuel additive of the present invention is characterized by containing ferrocene and / or a ferrocene derivative and lecithin.
- the solid fuel additive of the present invention is characterized by containing ferrocene and / or a ferrocene derivative of 80 to 99% by mass and lecithin of 1 to 20% by mass, and the particulate fuel additive of the present invention comprises ferrocene and It is characterized by containing 78 to 99% by mass of a ferrocene derivative, 0.9 to 20% by mass of lecithin, and 0.1 to 2% by mass of water.
- the liquid fuel additive of the present invention contains a mineral oil in which ferrocene and / or a ferrocene derivative and lecithin are dissolved, and the content of the ferrocene and / or ferrocene derivative is 2 to 5% by mass.
- the content of is characterized by being 5 to 50% by mass.
- the fuel additive of the present invention is used by being added so that the concentration of ferrocene and / or ferrocene derivative in the fuel is 1 to 50 ppm and the concentration of lecithin is 0.01 to 500 ppm. To do.
- the fuel additive of the present invention is a fuel additive containing ferrocene and / or a ferrocene derivative and lecithin.
- these fuel additives can be in a solid form, in particular, a particulate form and a liquid form.
- Ferrocene and ferrocene derivatives Ferrocene is formally called bis (cyclopentadienyl) iron and is also called dicyclopentadienyl iron.
- the ferrocene derivative used in the present invention is a compound having a structure having a substituent such as an alkyl group on the dicyclopentadienyl ring.
- ethyl ferrocene, butyl ferrocene, acetyl ferrocene, 2,2-bis-ethyl ferrocenyl propane, etc. Can be mentioned.
- ferrocenes Methods for producing ferrocene and its derivatives (hereinafter referred to as ferrocenes) include, for example, US Pat. No. 2,650,756, US Pat. No. 2,769,828, US Pat. No. 2,837,796, US Pat. It is disclosed in US Pat. No. 3,035,968, US Pat. No. 3,238,158, US Pat. No. 3,437,634, and the like.
- ferrocenes may be a solid such as fine powder, coarse particles, pellets, or a liquid, and can be appropriately selected depending on the form of the fuel additive of the present invention. This will be described in detail later.
- the fuel additive of the present invention can have a combustion promoting action, a dust reducing action, a NOX reducing action, and the like.
- a combustion promoting action that suppresses the formation of deposits on the valve, the piston ring, and the combustion chamber is seen by this combustion promoting action. Since this deposit reduces the output of the engine and increases the wear of the adhered parts, suppressing the formation of the deposit realizes a stable operation of the diesel engine. Further, by suppressing excess air during combustion by combustion reforming such as combustion promotion, dust reduction, NOX reduction, etc., fuel consumption can be reduced by several percent.
- Lecithin Lecithin is an animal or plant phospholipid mainly composed of glycerophospholipid and sphingophospholipid.
- Various vegetable oils such as soybean oil, rapeseed oil, rice bran oil, palm oil, sunflower oil, coconut oil, cottonseed oil, corn oil, peanut oil, linseed oil, safflower oil, olive oil and the like are obtained in the purification process.
- it contains 1 to 50% of vegetable oil, and there are liquids and solids at room temperature depending on the content of this vegetable oil and the ratio of saturated acid to unsaturated acid in the vegetable oil.
- powdered lecithin has been produced from liquid lecithin by oil extraction and vacuum drying.
- the lecithin may be a liquid or a solid such as a fine powder, and can be appropriately selected depending on the form of the fuel additive of the present invention. This will be described in detail later.
- the fuel additive of the present invention can take the form of solid, particulate and liquid.
- the solid fuel additive of the present invention preferably contains 80 to 99% ferrocenes and 1 to 20% lecithin. This is because if the lecithin is less than 1%, the ferrocenes may be difficult to dissolve in the fuel, and if the lecithin is contained in 20%, the effect of improving the solubility of the ferrocene can be sufficiently obtained.
- Ferrocenes are not particularly limited as long as they are solid at room temperature, and examples thereof include fine powders, coarse particles, and pellets.
- Lecithin is preferably in the form of a powder at normal temperature, and more preferably in the form of a fine powder having a particle diameter of 1 mm or less. This is because the mixing with ferrocenes can be more uniform.
- the particulate fuel additive of the present invention is one form of the solid fuel additive, and is obtained by granulating a fine powdered ferrocene compound into a coarse particle form.
- the particle size is preferably 0.5 mm to 15 mm, more preferably 1 mm to 10 mm. This is because if the particle size is less than 0.5 mm, workability may be inferior due to scattering, and if it exceeds 15 mm, the peptization may be lowered and the solubility may be lowered. It preferably contains 78-99% ferrocenes, 0.9-20% lecithin and 0.1-2% moisture.
- Ferrocenes are preferably in the form of a powder at normal temperature, and more preferably in the form of a fine powder having a particle diameter of 2 mm or less.
- Lecithin is also preferably in the form of a powder at normal temperature, and more preferably in the form of a fine powder having a particle diameter of 1 mm or less. This is for the convenience of granulation.
- the powdered lecithin used in the present invention has high hygroscopicity, and produces a tackiness suitable for granulation by mixing a small amount of moisture, but if the moisture content is less than 0.1%, sufficient tackiness may not occur. Yes, if it exceeds 2%, the water content becomes excessive and the powdered ferrocenes and the powdered lecithin may be agglomerated.
- the liquid fuel additive of the present invention contains a mineral oil in which ferrocene and / or a ferrocene derivative and lecithin are dissolved, and the content of the ferrocene and / or ferrocene derivative is 2 to Preferably, the lecithin content is 5 to 50%. If lecithin is less than 5%, ferrocenes may be difficult to dissolve in mineral oil, and if lecithin is contained in 50%, the effect of improving the solubility of ferrocene in mineral oil can be sufficiently obtained.
- Ferrocenes may be solid, such as fine powder, coarse particles, pellets, or liquid, but may be liquid or fine powder from the viewpoint of easy dissolution in mineral oil. preferable.
- the lecithin may be a liquid or a solid such as a fine powder, but is preferably a liquid or a fine powder that is easily dissolved in mineral oil.
- the mineral oil used in the present invention refers to hydrocarbon heavy oil, light oil, kerosene and the like.
- a heavy oil, B heavy oil, light oil, kerosene, etc. can be preferably used for C heavy oil used as fuel for large diesel engines for ships, and A heavy oil can be more preferably used.
- the lecithin in the present invention mainly has the following actions. i) Improvement of solubility and solubility of ferrocenes in fuel. ii) Dispersing action of sludge in fuel oil. iii) Binder action during granulation in the particulate fuel additive. iv) Peptization in particulate fuel additives. v) Improved solubility of ferrocenes in mineral oil in liquid fuel additives.
- fuel includes A heavy oil used as fuel oil for diesel engines, oil combustion furnaces, boilers, etc., light oil such as kerosene and light oil, heavy oil, heavy residual oil, lubricating oil, waste oil, and these
- these emulsion fuels, solid fuels such as coal, and the like can be used, but the fuel is not limited to these as long as the shape is a fuel other than gas.
- ferrocene alone has a very low solubility in petroleum solvents such as aromatic solvents and aliphatic solvents other than benzene, toluene and xylene, and only dissolves at a maximum concentration of 3% at 20 ° C.
- the ferrocene concentration of the long-term stable solution is preferably 2.5% or less.
- ferrocene is dissolved in fuel such as heavy oil.
- ferrocene can be dissolved to a concentration of 5%, and the stability of the solution becomes good in a wide temperature range.
- Table 1 shows the relationship between the maximum solubility of ferrocene in A heavy oil and the amount of lecithin added.
- ferrocenes can be easily dissolved in the fuel or fuel additive itself of various combustion facilities to obtain a stable solution, so that the ferrocenes can be uniformly distributed in the combustion engine. It becomes possible to spray in the form of fine particles. As a result, the effects of ferrocene can be fully exhibited.
- lecithin has a lipophilic part and a hydrophilic part, and thus is known to work as a surfactant.
- solubility and the like are improved by the action of the lipophilic part of lecithin. . That is, when ferrocenes and lecithin are dissolved in the fuel, a part of the lipophilic part of lecithin is immediately adsorbed on the surface of the ferrocene, and the other lipophilic part enhances the lipophilicity on the surface of the ferrocene. It is thought that it contributes to the improvement in solubility and solubility in fuel oil. These effects are not found in other surfactants such as nonionic surfactants with strong new oil properties, and are unique to lecithin.
- Sludge is an insoluble material present in heavy fuel oils in particular, and is liable to settle, causing strainer clogging troubles and poor combustion.
- the occurrence of this is that hydrocarbons remaining in the kettle residue oil are oxidized, polymerized, and condensed to change into high molecular weight hydrocarbons by heat treatment, catalytic cracking, thermal cracking, etc. in the refining process of crude oil. caused by.
- the above-mentioned changes occur in the order of hydrocarbon ⁇ marten ⁇ asphalten ⁇ carbene ⁇ carboid ⁇ carbon, and these macromolecules are initially present in heavy oil as a large molecular colloid.
- the colloid is considered to be composed of hydrocarbons with a very high C / H ratio, such as carbene and carboid, surrounded by some asphaltenes and further surrounded by polymer hydrocarbons with a low C / H ratio. It is done.
- Asphaltic substances present in heavy oil as such colloidal particles will not cause problems such as straining of the strainer and poor combustion without precipitating if they are dispersed in a stable colloidal form and floated.
- the colloidal particles are polar and adsorbable. Therefore, when the equilibrium state is lost due to heating, mixing with different oils, storage for a long time, etc., the colloidal particles are bonded one after another to form a large particle aggregate (micellar colloid), which precipitates to form sludge. .
- the polymer hydrocarbon and marten in the colloid surface layer are dissolved, but asphaltenes and carbides are unsaturated and polar.
- large asphaltene particles are bonded to each other to form sludge.
- the colloid surface layer dissolves, and the viscosity decreases as the temperature rises, so that particle motion becomes active, and asphaltene collides with each other to increase the chance of collision and sludge. Is formed.
- Lecithin permeates and adsorbs in sludge bonds and associations such as carbon and asphaltenes, and acts as a surfactant to subdivide the sludge with its dispersion force. This action also has the effect of preventing sludge precipitation by preventing mixing of different fuels and bonding of colloidal particles due to heating.
- Binder action during granulation in the particulate fuel additive As described above, when granulating the particulate fuel additive, lecithin is mixed with a small amount of water, thereby producing an adhesive suitable for granulation, and serves as a binder.
- the lecithin contained in the particulate fuel additive has a peptizing action that makes the particles easy to break when the additive is added to the fuel.
- the crushed additive is further easily dissolved by the lecithin solubility improving effect.
- the fuel additive of the present invention is a ferrocene concentration in various fuels used in diesel engines, oil combustion furnaces, boiler devices, etc. used in ships and power generation facilities. Is preferably added so that the concentration of lecithin is 0.01 to 500 ppm. More specifically, it is usually preferable to continuously inject the ferrocene so that the concentration of ferrocene is 1 to 10 ppm in an oil combustion furnace and a boiler device and 10 to 50 ppm in a diesel engine. However, depending on the state of the combustion engine, when trying to significantly improve the intended combustion acceleration effect, dust reduction effect, NOx reduction effect, etc., the amount of this continuous injection is temporarily several to several tens of times larger. It can be injected for a short time.
- the concentration of lecithin is an advantageous concentration for easily and stably dissolving ferrocenes in the fuel oil and the fuel additive itself.
- heavy fuel oil is used to further disperse sludge.
- the solid fuel additives (Examples 1 to 4) of the present invention have a very high dissolution rate until the ferrocene concentration reaches 3%, as compared with Comparative Example 1. Further, the concentration of the stable solution was 3% in Comparative Example 1 and a large amount of insoluble matter, whereas in Examples 1 to 4, a concentration of 3.5 to 5.0% became possible. Furthermore, the stability evaluation after 1 week of Examples 1 to 4 resulted in excellent or good. As described above, the solid fuel additive of the present invention was found to be very excellent in all aspects of ferrocene dissolution rate, dissolution concentration, and stability evaluation.
- the liquid fuel additives of the present invention were compared with Comparative Example 2 in the dissolution rate until a predetermined amount of ferrocene was completely dissolved in the heavy oil A at the time of preparation of the fuel additive. Is very fast. Furthermore, the stability evaluation after one week resulted in excellent or good. As described above, the liquid fuel additive of the present invention was found to be very excellent in all aspects of ferrocene dissolution rate, dissolution concentration, and stability evaluation.
- Examples 1 to 4 and the liquid fuel additive of the present invention were excellent in sludge as compared with Comparative Examples 1 and 2 and no additive. Has a dispersion effect. In Comparative Examples 1 and 2 that did not contain lecithin, no effect was observed, which was the same as the additive-free C heavy oil. The effect of lecithin was almost proportional to the amount added.
- the TG (thermogravimetric analysis) residual char combustion rate constant was calculated from the mass decrease curve of the generated residual charcoal when retained (the mass at the 95% burn-off point is m2).
- the amount of air was 100 ml / min.
- the following formula (I) was used for the calculation method.
- ferrocene and / or a ferrocene derivative together with lecithin, it is possible to provide a fuel additive in which the contained ferrocene and / or ferrocene derivative can be easily and stably dissolved in fuel. .
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Liquid Carbonaceous Fuels (AREA)
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Abstract
Description
フェロセンは一般に固体状であり、特に固体状フェロセンを溶解させるには、固体の大きさにも依存するが、かなりの攪拌力と時間を必要とする。僅かな添加量でも簡単には溶けず、燃料に添加する前に予め溶解しなければ内燃機関にトラブルが発生するため、攪拌機付き溶解タンクで溶剤に溶かしてから燃料に添加しているのが現状である。 However, the ferrocene and ferrocene derivatives used in these inventions have the disadvantage that their solubility in aromatic solvents, aliphatic solvents and petroleum solvents is very low.
Ferrocene is generally in a solid state. In particular, it takes considerable stirring power and time to dissolve solid ferrocene, depending on the size of the solid. Even if a small amount is added, it does not dissolve easily, and if it does not dissolve in advance before it is added to the fuel, problems will occur in the internal combustion engine. Therefore, it is currently dissolved in a solvent in a dissolution tank with a stirrer and then added to the fuel. It is.
フェロセンは、正式にはビス(シクロペンタジエニル)鉄といい、またジシクロペンタジエニル鉄とも呼ばれる。本発明で用いるフェロセン誘導体は、ジシクロペンタジエニル環にアルキル基等の置換基を有する構造の化合物であり、例えばエチルフェロセン、ブチルフェロセン、アセチルフェロセン、2,2-ビスーエチルフェロセニルプロパン等を挙げることができる。 (1) Ferrocene and ferrocene derivatives Ferrocene is formally called bis (cyclopentadienyl) iron and is also called dicyclopentadienyl iron. The ferrocene derivative used in the present invention is a compound having a structure having a substituent such as an alkyl group on the dicyclopentadienyl ring. For example, ethyl ferrocene, butyl ferrocene, acetyl ferrocene, 2,2-bis-ethyl ferrocenyl propane, etc. Can be mentioned.
レシチンは、グリセロリン脂質及びスフィンゴリン脂質を主成分とする動植物リン脂質である。各種の植物油、例えば大豆油、菜種油、米ぬか油、パーム油、ヒマワリ油、ヤシ油、綿実油、トウモロコシ油、落花生油、アマニ油、サフラワー油、オリーブ油等の精製工程で得られる。通常、植物油を1~50%含んでおり、この植物油の含有量や、植物油中の飽和酸と不飽和酸との比率に応じて、常温で液体と固体のものが存在する。また、近年は、油分抽出・真空乾燥することによって、液体レシチンから粉末レシチンが製造されている。 (2) Lecithin Lecithin is an animal or plant phospholipid mainly composed of glycerophospholipid and sphingophospholipid. Various vegetable oils such as soybean oil, rapeseed oil, rice bran oil, palm oil, sunflower oil, coconut oil, cottonseed oil, corn oil, peanut oil, linseed oil, safflower oil, olive oil and the like are obtained in the purification process. Usually, it contains 1 to 50% of vegetable oil, and there are liquids and solids at room temperature depending on the content of this vegetable oil and the ratio of saturated acid to unsaturated acid in the vegetable oil. In recent years, powdered lecithin has been produced from liquid lecithin by oil extraction and vacuum drying.
本発明の燃料添加剤は、固体状、粒子状及び液体状の形態をとることができる。 (3) Form of fuel additive The fuel additive of the present invention can take the form of solid, particulate and liquid.
本発明の固体状燃料添加剤は、80~99%のフェロセン類と1~20%のレシチンとを含むことが好ましい。レシチンが1%未満ではフェロセン類が燃料に溶解し難いことがあり、レシチンを20%含有すれば十分にフェロセン類の溶解性向上の効果が生じ得るからである。
フェロセン類は、常温において固体の形態であれば特に限定されるものではなく、例えば微粉末状、粗粒子状、ペレット状などの形態を挙げることができる。またレシチンは、常温において粉末状の形態であることが好ましく、更に好ましくは粒子径が1mm以下の微粉末状の形態である。フェロセン類との混合がより均一になり得るからである。 (I) Solid fuel additive The solid fuel additive of the present invention preferably contains 80 to 99% ferrocenes and 1 to 20% lecithin. This is because if the lecithin is less than 1%, the ferrocenes may be difficult to dissolve in the fuel, and if the lecithin is contained in 20%, the effect of improving the solubility of the ferrocene can be sufficiently obtained.
Ferrocenes are not particularly limited as long as they are solid at room temperature, and examples thereof include fine powders, coarse particles, and pellets. Lecithin is preferably in the form of a powder at normal temperature, and more preferably in the form of a fine powder having a particle diameter of 1 mm or less. This is because the mixing with ferrocenes can be more uniform.
本発明の粒子状燃料添加剤は、上記固体状燃料添加剤の一形態であり、微粉末状フェロセン化合物を、粗粒子状に造粒したものである。その粒径は0.5mm~15mmであることが好ましく、より好ましくは1mm~10mmである。粒径が0.5mm未満では、飛散のために作業性が劣る場合があり、15mmを超えると解膠性が低下して溶解性が下がる可能性があるからである。
78~99%のフェロセン類、0.9~20%のレシチン及び0.1~2%の水分を含むことが好ましい。レシチンが0.9%未満ではフェロセン類が燃料に溶解し難いことがあり、レシチンを20%含有すれば十分にフェロセン類の溶解性向上の効果が生じ得るからである。
フェロセン類は、常温において粉末状の形態であることが好ましく、更に好ましくは粒子径が2mm以下の微粉末状の形態である。またレシチンも、常温において粉末状の形態であることが好ましく、更に好ましくは粒子径が1mm以下の微粉末状の形態である。造粒の便宜のためである。
本発明において使用する粉末状レシチンは吸湿性が高く、少量の水分を混合することで造粒に適する粘着性を生じるが、水分が0.1%未満では十分な粘着性が生じない可能性があり、2%を超えると水分が過剰となり上記粉末状フェロセン類及び上記粉末状レシチンが塊状化する恐れがある。 (Ii) Particulate fuel additive The particulate fuel additive of the present invention is one form of the solid fuel additive, and is obtained by granulating a fine powdered ferrocene compound into a coarse particle form. The particle size is preferably 0.5 mm to 15 mm, more preferably 1 mm to 10 mm. This is because if the particle size is less than 0.5 mm, workability may be inferior due to scattering, and if it exceeds 15 mm, the peptization may be lowered and the solubility may be lowered.
It preferably contains 78-99% ferrocenes, 0.9-20% lecithin and 0.1-2% moisture. This is because if lecithin is less than 0.9%, ferrocenes may be difficult to dissolve in the fuel, and if lecithin is contained in 20%, the effect of improving the solubility of ferrocene can be sufficiently obtained.
Ferrocenes are preferably in the form of a powder at normal temperature, and more preferably in the form of a fine powder having a particle diameter of 2 mm or less. Lecithin is also preferably in the form of a powder at normal temperature, and more preferably in the form of a fine powder having a particle diameter of 1 mm or less. This is for the convenience of granulation.
The powdered lecithin used in the present invention has high hygroscopicity, and produces a tackiness suitable for granulation by mixing a small amount of moisture, but if the moisture content is less than 0.1%, sufficient tackiness may not occur. Yes, if it exceeds 2%, the water content becomes excessive and the powdered ferrocenes and the powdered lecithin may be agglomerated.
本発明の液体状燃料添加剤は、フェロセン及び/又はフェロセン誘導体とレシチンとを溶解させた鉱物油を含有し、該フェロセン及び/又はフェロセン誘導体の含有量が2~5%、該レシチンの含有量が5~50%であることが好ましい。レシチンが5%未満ではフェロセン類が鉱物油に溶解し難いことがあり、レシチンを50%含有すれば十分に鉱物油に対するフェロセン類の溶解性向上の効果が生じ得るからである。
フェロセン類は、微粉末状、粗粒子状、ペレット状等の固体であっても、液体であってもよいが、鉱物油に溶解させやすい形状という観点から、液体又は微粉末状であることが好ましい。また、レシチンも同様に液体であっても微粉末状等の固体であってもよいが、鉱物油に溶解させやすい形状である液体又は微粉末状であることが好ましい。
なお、本発明において使用される鉱物油とは、炭化水素系の重油、軽油、灯油等をいう。例えば、船舶用の大型ディーゼルエンジン等の燃料として用いられるC重油に対しては、A重油、B重油、軽油、灯油等を好ましく用いることができ、更に好ましくはA重油を用いることができる。 (Iii) Liquid fuel additive The liquid fuel additive of the present invention contains a mineral oil in which ferrocene and / or a ferrocene derivative and lecithin are dissolved, and the content of the ferrocene and / or ferrocene derivative is 2 to Preferably, the lecithin content is 5 to 50%. If lecithin is less than 5%, ferrocenes may be difficult to dissolve in mineral oil, and if lecithin is contained in 50%, the effect of improving the solubility of ferrocene in mineral oil can be sufficiently obtained.
Ferrocenes may be solid, such as fine powder, coarse particles, pellets, or liquid, but may be liquid or fine powder from the viewpoint of easy dissolution in mineral oil. preferable. Similarly, the lecithin may be a liquid or a solid such as a fine powder, but is preferably a liquid or a fine powder that is easily dissolved in mineral oil.
The mineral oil used in the present invention refers to hydrocarbon heavy oil, light oil, kerosene and the like. For example, A heavy oil, B heavy oil, light oil, kerosene, etc. can be preferably used for C heavy oil used as fuel for large diesel engines for ships, and A heavy oil can be more preferably used.
本発明におけるレシチンは、主に次の作用を担う。
i)燃料に対するフェロセン類の溶解性及び溶解度の向上。
ii)燃料油中のスラッジの分散作用。
iii)粒子状燃料添加剤における造粒時のバインダー作用。
iv)粒子状燃料添加剤における解膠作用。
v)液体状燃料添加剤におけるフェロセン類の鉱物油に対する溶解性の向上。
以下に、上記の各々の作用について説明する。 (4) Action and effect of lecithin The lecithin in the present invention mainly has the following actions.
i) Improvement of solubility and solubility of ferrocenes in fuel.
ii) Dispersing action of sludge in fuel oil.
iii) Binder action during granulation in the particulate fuel additive.
iv) Peptization in particulate fuel additives.
v) Improved solubility of ferrocenes in mineral oil in liquid fuel additives.
Hereinafter, each of the above operations will be described.
上述のようにフェロセン類は、各種燃料に対する溶解性及び溶解度が低いという欠点を有している。ここで「燃料」としては、ディーゼルエンジン、油燃焼炉及びボイラー装置等の燃料油として用いられるA重油、灯油や軽油等の軽質油、重質油、重質残渣油、潤滑油、廃油及びこれらの混合油、更にこれらのエマルション燃料、また石炭等の固体燃料等を挙げることができるが、形状が気体以外の燃料であればこれらに限定されるものではない。 (I) Improvement of Solubility and Solubility of Ferrocenes in Fuel As described above, ferrocenes have a drawback of low solubility and solubility in various fuels. Here, “fuel” includes A heavy oil used as fuel oil for diesel engines, oil combustion furnaces, boilers, etc., light oil such as kerosene and light oil, heavy oil, heavy residual oil, lubricating oil, waste oil, and these In addition, these emulsion fuels, solid fuels such as coal, and the like can be used, but the fuel is not limited to these as long as the shape is a fuel other than gas.
A重油に対するフェロセン最大溶解度とレシチン添加量との関係を表1に示す。 For example, ferrocene alone has a very low solubility in petroleum solvents such as aromatic solvents and aliphatic solvents other than benzene, toluene and xylene, and only dissolves at a maximum concentration of 3% at 20 ° C. The ferrocene concentration of the long-term stable solution is preferably 2.5% or less. The same applies when ferrocene is dissolved in fuel such as heavy oil. However, by adding a predetermined amount of lecithin, ferrocene can be dissolved to a concentration of 5%, and the stability of the solution becomes good in a wide temperature range.
Table 1 shows the relationship between the maximum solubility of ferrocene in A heavy oil and the amount of lecithin added.
これらの作用は、新油性の強い非イオン系界面活性剤など他の界面活性剤には見られず、レシチン固有の特異性である。 It is known that lecithin has a lipophilic part and a hydrophilic part, and thus is known to work as a surfactant. In the present invention, it is considered that solubility and the like are improved by the action of the lipophilic part of lecithin. . That is, when ferrocenes and lecithin are dissolved in the fuel, a part of the lipophilic part of lecithin is immediately adsorbed on the surface of the ferrocene, and the other lipophilic part enhances the lipophilicity on the surface of the ferrocene. It is thought that it contributes to the improvement in solubility and solubility in fuel oil.
These effects are not found in other surfactants such as nonionic surfactants with strong new oil properties, and are unique to lecithin.
この作用は、上述のフェロセン類の溶解促進作用とは異なり、レシチン自体が燃料添加剤として働き、ディーゼルエンジンを始めとする燃焼設備の長期安定運転に寄与するものである。 ii) Dispersing action of sludge in fuel oil.
This action is different from the above-mentioned accelerating action of ferrocenes, and lecithin itself acts as a fuel additive, contributing to the long-term stable operation of combustion facilities such as diesel engines.
上述のように、粒子状燃料添加剤を造粒する際にレシチンは少量の水分と混合されることで造粒に適する粘着性を生じ、バインダーとしての役割を担う。 iii) Binder action during granulation in the particulate fuel additive.
As described above, when granulating the particulate fuel additive, lecithin is mixed with a small amount of water, thereby producing an adhesive suitable for granulation, and serves as a binder.
粒子状燃料添加剤に含まれるレシチンは、添加剤を燃料に投入した際に粒子が砕けやすくする解膠作用を有する。砕かれた添加剤は、更にレシチンの溶解性向上作用により非常に溶解しやすくなる。 iv) Peptization in particulate fuel additives.
The lecithin contained in the particulate fuel additive has a peptizing action that makes the particles easy to break when the additive is added to the fuel. The crushed additive is further easily dissolved by the lecithin solubility improving effect.
フェロセン類は、鉱物油に対する溶解度が非常に低く、約2.5%の濃度までしか溶解しない。しかし、所定量のレシチンを添加することによって、フェロセンを5%の濃度まで溶解することが可能となり、その溶液の安定性は幅広い温度域で良好となる。 v) Improved solubility of ferrocenes in mineral oil in liquid fuel additives.
Ferrocenes have very low solubility in mineral oil and only dissolve to a concentration of about 2.5%. However, by adding a predetermined amount of lecithin, ferrocene can be dissolved to a concentration of 5%, and the stability of the solution is good in a wide temperature range.
本発明の燃料添加剤は、船舶や発電設備等で使用されるディーゼルエンジン、油燃焼炉及びボイラー装置等に用いる各種燃料において、フェロセン類の濃度が1~50ppm、レシチンの濃度が0.01~500ppmとなるように添加して使用することが好ましい。
更に詳しくは、通常は、フェロセン類の濃度について、油燃焼炉及びボイラー装置では1~10ppm、ディーゼルエンジンでは10~50ppmとなるように連続注入して用いることが好ましい。
ただし、燃焼機関の状態によっては、目的とする燃焼促進作用、煤塵減少作用、NOX低減作用等を大幅に改善させようとする場合に、この連続注入量の数~数十倍量を一時的に短時間注入することができる。 (5) Concentration of ferrocenes and lecithin in fuel The fuel additive of the present invention is a ferrocene concentration in various fuels used in diesel engines, oil combustion furnaces, boiler devices, etc. used in ships and power generation facilities. Is preferably added so that the concentration of lecithin is 0.01 to 500 ppm.
More specifically, it is usually preferable to continuously inject the ferrocene so that the concentration of ferrocene is 1 to 10 ppm in an oil combustion furnace and a boiler device and 10 to 50 ppm in a diesel engine.
However, depending on the state of the combustion engine, when trying to significantly improve the intended combustion acceleration effect, dust reduction effect, NOx reduction effect, etc., the amount of this continuous injection is temporarily several to several tens of times larger. It can be injected for a short time.
なお、各種特性の評価は下記の要領で行った。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
Various characteristics were evaluated in the following manner.
固体状燃料添加剤(実施例1~4・比較例1)
燃料油としてのA重油(硫黄分=0.09%、粘度=2.8cst(50℃))200gに対し、20℃、60rpmで攪拌しながらフェロセンを添加し、フェロセン濃度が3%に至るまでの溶解速度を秒数で評価した。引き続き、更にフェロセンを添加して安定な溶解液を最大濃度で作製し、室温に静置して1週間後の状態で安定性を評価した。結果を表2に示す。
液体状燃料添加剤(実施例5~7・比較例2)
20℃、60rpmで攪拌しながら、表3の配合で調製した燃料添加剤について、A重油にフェロセンが完全に溶解するまでの溶解速度を秒数で評価した。得られた溶解液を室温にて静置して1週間後の状態で安定性を評価した。試験は200gスケールで行った。結果を表3に示す。 [Evaluation by solubility test of ferrocene]
Solid fuel additive (Examples 1 to 4 and Comparative Example 1)
Ferrocene is added to 200 g of heavy oil A (sulfur content = 0.09%, viscosity = 2.8 cst (50 ° C)) as fuel oil while stirring at 20 ° C and 60 rpm until the ferrocene concentration reaches 3%. The dissolution rate was evaluated in seconds. Subsequently, ferrocene was further added to prepare a stable solution at the maximum concentration, and the stability was evaluated in a state one week after standing at room temperature. The results are shown in Table 2.
Liquid fuel additive (Examples 5 to 7 and Comparative Example 2)
While stirring at 20 ° C. and 60 rpm, the dissolution rate until the ferrocene was completely dissolved in the heavy oil A was evaluated in seconds for the fuel additives prepared with the formulation shown in Table 3. The obtained lysate was allowed to stand at room temperature, and stability was evaluated in a state one week later. The test was conducted on a 200 g scale. The results are shown in Table 3.
本発明の固体状燃料添加剤(実施例1~4)は、比較例1と比較して、フェロセン濃度が3%に至るまでの溶解速度が非常に速い。また安定な溶解液の濃度について、比較例1が3%で不溶物が多い状態であるのに対し、実施例1~4では3.5~5.0%の濃度が可能となった。更に、実施例1~4の1週間後の安定性評価は、優又は良との結果となった。このように本発明の固体状燃料添加剤は、フェロセンの溶解速度、溶解濃度、安定性評価の全ての面において非常に優れていることが認められた。
本発明の液体状燃料添加剤(実施例5~7)は、比較例2と比較して、燃料添加剤の調製時において、A重油に対し所定量のフェロセンが完全溶解に至るまでの溶解速度が非常に速い。更に、1週間後の安定性評価は、優又は良との結果となった。このように本発明の液体燃料添加剤は、フェロセンの溶解速度、溶解濃度、安定性評価の全ての面において非常に優れていることが認められた。 Results The solid fuel additives (Examples 1 to 4) of the present invention have a very high dissolution rate until the ferrocene concentration reaches 3%, as compared with Comparative Example 1. Further, the concentration of the stable solution was 3% in Comparative Example 1 and a large amount of insoluble matter, whereas in Examples 1 to 4, a concentration of 3.5 to 5.0% became possible. Furthermore, the stability evaluation after 1 week of Examples 1 to 4 resulted in excellent or good. As described above, the solid fuel additive of the present invention was found to be very excellent in all aspects of ferrocene dissolution rate, dissolution concentration, and stability evaluation.
The liquid fuel additives of the present invention (Examples 5 to 7) were compared with Comparative Example 2 in the dissolution rate until a predetermined amount of ferrocene was completely dissolved in the heavy oil A at the time of preparation of the fuel additive. Is very fast. Furthermore, the stability evaluation after one week resulted in excellent or good. As described above, the liquid fuel additive of the present invention was found to be very excellent in all aspects of ferrocene dissolution rate, dissolution concentration, and stability evaluation.
表2及び表3に記載の実施例及び比較例を用いてスラッジ分散試験を行った。
試験は日本船主協会法に準じて行った。 [Sludge dispersion effect]
Sludge dispersion tests were performed using the examples and comparative examples described in Tables 2 and 3.
The test was conducted according to the Japan Shipowners Association Act.
(1)C重油0.1gを試験管に採り、これにノルマルヘプタン20mlを加えた。これに実施例1~7及び比較例1~2の燃料添加剤を0.02ml(1/1000)添加した。
(2)試験管に栓をして完全に混ざるまで20回以上強く振とうした。
(3)これを室温で静置し、経過時間毎の分散状態を、次の基準によって判定した。 Operating procedure (1) 0.1 g of C heavy oil was put in a test tube, and 20 ml of normal heptane was added thereto. To this, 0.02 ml (1/1000) of the fuel additives of Examples 1 to 7 and Comparative Examples 1 and 2 were added.
(2) The test tube was capped and shaken vigorously 20 times or more until completely mixed.
(3) This was left still at room temperature, and the dispersion | distribution state for every elapsed time was determined by the following reference | standard.
A…完全に分散し沈殿のないもの。
B…分散はしているが沈殿のあるもの。
沈殿量の少ないものから順に、B1、B2、B3とする。
C…分散しないもの(ほとんど沈殿しているもの)。
試験結果を表4に示す。 Judgment criteria A: completely dispersed and no precipitation.
B: Dispersed but precipitated.
B1, B2, and B3 are set in ascending order of precipitation amount.
C: No dispersion (almost precipitated).
The test results are shown in Table 4.
本発明の固体状燃料添加剤(実施例1~4)及び本発明の液体状燃料添加剤(実施例5~7)は、比較例1、2及び無添加と比較して極めて優れたスラッジ分散効果を有する。レシチンを含有しない比較例1、2では全く効果が見られず、無添加のC重油と同じであった。レシチンの効果は、概ね添加量に比例した結果であった。 Results The solid fuel additive of the present invention (Examples 1 to 4) and the liquid fuel additive of the present invention (Examples 5 to 7) were excellent in sludge as compared with Comparative Examples 1 and 2 and no additive. Has a dispersion effect. In Comparative Examples 1 and 2 that did not contain lecithin, no effect was observed, which was the same as the additive-free C heavy oil. The effect of lecithin was almost proportional to the amount added.
本発明の液体状燃料添加剤(実施例5~7)及び比較例2の液体状燃料添加剤を添加した燃料油(C重油…上記スラッジ分散効果の評価に用いたものと同じ)10mgを示差熱天秤TG/DTA6300(セイコーインスツメンツ株式会社製)を用いて、昇温速度100℃/分にて500℃まで加熱燃焼させ(残炭生成終了点での質量をm1とする)500℃で保持した時の生成残炭(95%燃えきり点の質量をm2とする)の質量減少曲線からTG(熱重量分析)残炭燃焼速度定数を算出した。空気量は100ml/分で行った。算出方法には次式(I)を用いた。※1、※2
TG残炭燃焼速度定数=A×T×In(m1/m2)/τ・・・(I)
A :定数
T :温度
m1:残炭生成終了点での質量
m2:95%燃えきり点の質量
τ :(m2-m1)時間
※1 柴山ら、日本機械学会論文集、34(260)、769(1968)
※2 候ら、日本機械学会論文集、54(507)3301(1988)
試験結果を表5に示す。 [Measurement of burning rate]
10 mg of fuel oil to which the liquid fuel additive of the present invention (Examples 5 to 7) and the liquid fuel additive of Comparative Example 2 were added (C heavy oil: same as that used in the evaluation of the sludge dispersion effect) Using a thermobalance TG / DTA6300 (manufactured by Seiko Instruments Inc.), it is heated and combusted to 500 ° C. at a rate of temperature increase of 100 ° C./min (the mass at the end of the residual coal production is m1) at 500 ° C. The TG (thermogravimetric analysis) residual char combustion rate constant was calculated from the mass decrease curve of the generated residual charcoal when retained (the mass at the 95% burn-off point is m2). The amount of air was 100 ml / min. The following formula (I) was used for the calculation method. * 1, * 2
TG residual char combustion rate constant = A × T × In (m1 / m2) / τ (I)
A: Constant T: Temperature m1: Mass at the end of residual coal generation m2: Mass at the 95% burnout point τ: (m2-m1) time * 1 Shibayama et al., Transactions of the Japan Society of Mechanical Engineers, 34 (260), 769 (1968)
* 2 Kyoka et al., Transactions of the Japan Society of Mechanical Engineers, 54 (507) 3301 (1988)
The test results are shown in Table 5.
本発明の液体状燃料添加剤(実施例5~7)の1000ppm添加は、比較例2の1000ppm添加と比較して高いTG残炭燃焼速度定数(相対速度定数)が得られた。これはフェロセンの含有量が多いので当然の結果であるが、実施例5~7の500ppm添加でも比較例2の1000ppm添加よりも高いTG残炭燃焼速度定数(相対速度定数)が得られた。更に、実施例5~7の1000ppm添加では、比較例2の2000ppm添加よりも高いTG残炭燃焼速度定数(相対速度定数)が得られた。
これはレシチンのフェロセンに対する溶解度の向上とスラッジ分散効果との相乗効果と推察できる。レシチンを含有しない比較例2ではフェロセンは添加剤液中で不安定であるので燃料油中でも溶解が不十分と考えられる。また、スラッジ分散効果もないために、フェロセンの相対含有量が同じ場合、実施例5~7と比較して効果が劣ったと思われる。 Results The 1000 ppm addition of the liquid fuel additive of the present invention (Examples 5 to 7) resulted in a higher TG residual char combustion rate constant (relative rate constant) than the 1000 ppm addition of Comparative Example 2. This is a natural result because the content of ferrocene is large, but even with the addition of 500 ppm in Examples 5 to 7, a higher TG residual carbon combustion rate constant (relative rate constant) was obtained than with the addition of 1000 ppm in Comparative Example 2. Further, with the addition of 1000 ppm in Examples 5 to 7, a TG residual char combustion rate constant (relative rate constant) higher than that with the addition of 2000 ppm in Comparative Example 2 was obtained.
This can be inferred to be a synergistic effect of the improvement in the solubility of lecithin in ferrocene and the sludge dispersion effect. In Comparative Example 2 that does not contain lecithin, ferrocene is unstable in the additive solution, so that it is considered that the ferrocene is insufficiently dissolved in the fuel oil. Also, since there is no sludge dispersion effect, it seems that the effect is inferior compared with Examples 5 to 7 when the relative content of ferrocene is the same.
本発明の固体状燃料添加剤(実施例3)及び比較例1の固体状燃料添加剤を用いて、ディーゼルエンジンを備えた下記の仕様の貨物船で実機試験を行った。実機試験は、攪拌機付溶解タンク内で、固体燃料添加剤9.0Kgを360リットルのA重油に溶解させ、次いで、該溶解タンクから注入ポンプで燃料(C重油)ラインに1/1000添加して行った(燃料添加剤の添加量は25ppm)。
実施例3と比較例1の固体状燃料添加剤について、1ヶ月(30日)ごとに交互に4ヶ月に渡って上記の方法で添加を行い(各固体燃料添加剤について、1ヶ月間×2回)、燃料消費量及び熱交換機の汚れ具合を目視観察して比較した。その後、水洗浄を行い汚れの除去性を比較した。 [Real machine test with diesel engine]
Using the solid fuel additive of the present invention (Example 3) and the solid fuel additive of Comparative Example 1, an actual machine test was conducted on a cargo ship having the following specifications equipped with a diesel engine. In the actual machine test, 9.0 kg of solid fuel additive was dissolved in 360 liters of A heavy oil in a dissolution tank with a stirrer, and then 1/1000 was added from the dissolution tank to the fuel (C heavy oil) line with an injection pump. (The amount of fuel additive added was 25 ppm).
The solid fuel additive of Example 3 and Comparative Example 1 was added by the above method alternately for 4 months every month (30 days) (for each solid fuel additive, 1 month × 2 Times), fuel consumption and heat exchanger contamination were visually observed and compared. Then, it washed with water and compared the removal property of dirt.
総トン数 :160,000トン
載貨重量トン数 :300,500トン
連続最大出力 :21,300KW×74rpm
シリンダー数 :10個
ターボ過給機の回転数 :10,000rpm
燃料消費量 :90,000L/day(無添加時)
試験結果を表6に示す。 Total tonnage of cargo ship : 160,000 tons Load tonnage: 300,500 tons Continuous maximum output: 21,300 KW x 74 rpm
Number of cylinders: 10 Rotation speed of turbocharger: 10,000 rpm
Fuel consumption: 90,000 L / day (without addition)
The test results are shown in Table 6.
本発明の固体燃料添加剤(実施例3)では、フェロセン自体の添加量は比較例1よりも僅かに少ないにも関わらず、燃料消費量が少ない結果となった。これは、レシチンがフェロセンの溶解性及び溶解度を向上させ、更にレシチン自体のスラッジ分散効果により、微細で安定した燃料噴霧が実現することで、総合的かつ相乗的に燃焼効率が向上したものである。また、燃焼促進作用が向上したため、熱交換機の汚れも比較例1に比べて清浄であり、簡単な水洗で除去されるという優位性がみられた。
その裏付けとして、実施例3の燃料添加剤を溶解タンク内に溶解させた場合、投入後、速やかに崩壊分散して約10分で完全に溶解し、また試験中も溶解タンク内には全く沈殿物・浮遊物は観られないことが確認された。それに対して、比較例1の燃料添加剤は約30分攪拌後に一部浮遊物が観られ、試験中も溶解タンク内はフェロセン不溶解分の沈殿・浮遊物が観られた。 Since it is a test on an actual ship, fuel consumption is affected by wind, tide flow, output differences, etc., but it can be judged that the evaluation is correct because the same results were obtained in both tests for each item.
In the solid fuel additive of the present invention (Example 3), although the amount of ferrocene added was slightly smaller than that in Comparative Example 1, the result was that the amount of fuel consumed was small. This is because lecithin improves the solubility and solubility of ferrocene, and further realizes a fine and stable fuel spray by the sludge dispersion effect of lecithin itself, thereby improving combustion efficiency comprehensively and synergistically. . Moreover, since the combustion promoting action was improved, the heat exchanger was clean as compared with Comparative Example 1, and the superiority of being removed by simple water washing was observed.
As a support for this, when the fuel additive of Example 3 was dissolved in the dissolution tank, it quickly disintegrated and dispersed after the addition, and completely dissolved in about 10 minutes. It was confirmed that no objects / floats were seen. On the other hand, the fuel additive of Comparative Example 1 was partially suspended after stirring for about 30 minutes, and during the test, precipitates and suspended solids insoluble in ferrocene were observed in the dissolution tank.
Claims (5)
- フェロセン及び/又はフェロセン誘導体とレシチンとを含有することを特徴とする燃料添加剤。 A fuel additive comprising ferrocene and / or a ferrocene derivative and lecithin.
- 上記フェロセン及び/又はフェロセン誘導体を80~99質量%、上記レシチンを1~20質量%含有し、固体状であることを特徴とする請求項1に記載の燃料添加剤。 2. The fuel additive according to claim 1, wherein the fuel additive contains 80 to 99% by mass of the ferrocene and / or ferrocene derivative and 1 to 20% by mass of the lecithin and is solid.
- 上記フェロセン及び/又はフェロセン誘導体を78~99質量%、上記レシチンを0.9~20質量%、水分を0.1~2質量%含有し、粒子状であることを特徴とする請求項1に記載の燃料添加剤。 The ferrocene and / or the ferrocene derivative is 78 to 99% by mass, the lecithin is 0.9 to 20% by mass, and the water is 0.1 to 2% by mass, and is in the form of particles. The fuel additive as described.
- 上記フェロセン及び/又はフェロセン誘導体と上記レシチンとを溶解させた鉱物油を含有する燃料添加剤であって、
上記フェロセン及び/又はフェロセン誘導体の含有量が2~5質量%、上記レシチンの含有量が5~50質量%であり、液体状であることを特徴とする請求項1に記載の燃料添加剤。 A fuel additive containing a mineral oil in which the ferrocene and / or ferrocene derivative and the lecithin are dissolved,
2. The fuel additive according to claim 1, wherein the content of the ferrocene and / or the ferrocene derivative is 2 to 5% by mass, the content of the lecithin is 5 to 50% by mass, and the fuel additive is liquid. - 燃料中の上記フェロセン及び/又はフェロセン誘導体の濃度が1~50ppm、且つ上記レシチンの濃度が0.01~500ppmとなるように添加して使用されることを特徴する請求項1~4のいずれかの項に記載の燃料添加剤。 5. The fuel according to claim 1, wherein the ferrocene and / or ferrocene derivative in the fuel is added so that the concentration thereof is 1 to 50 ppm and the lecithin concentration is 0.01 to 500 ppm. The fuel additive according to the section.
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CN2008800002688A CN101541930B (en) | 2008-01-16 | 2008-02-21 | Fuel additives |
EP08711738A EP2107103B1 (en) | 2008-01-16 | 2008-02-21 | Fuel additives |
DK08711738.8T DK2107103T3 (en) | 2008-01-16 | 2008-02-21 | Additives to fuels |
ES08711738T ES2383623T3 (en) | 2008-01-16 | 2008-02-21 | Fuel additives |
AT08711738T ATE553172T1 (en) | 2008-01-16 | 2008-02-21 | FUEL ADDITIVES |
US12/305,317 US20100050503A1 (en) | 2008-01-16 | 2008-02-21 | Fuel additive |
TW097142782A TWI408222B (en) | 2008-01-16 | 2008-11-06 | Fuel additive |
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CN102153596A (en) * | 2010-01-27 | 2011-08-17 | 阿莎康姆集团投资公司 | Method for production of metallocenes preventing nitrogen oxides emission in combustion of fuels in motors |
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JP4131748B1 (en) * | 2008-01-16 | 2008-08-13 | 株式会社タイホーコーザイ | Fuel additive |
JP2010163529A (en) * | 2009-01-15 | 2010-07-29 | Taihokohzai:Kk | Fuel additive |
US8513153B2 (en) * | 2009-04-22 | 2013-08-20 | Uto Environmental Products Limited | Fuel additive |
JP5607098B2 (en) * | 2012-03-29 | 2014-10-15 | Molエンジニアリング株式会社 | Powder or granule melting device |
CN103710070B (en) * | 2014-01-02 | 2015-06-03 | 江西智仁节能科技有限公司 | Coal economizing agent |
KR20200005260A (en) | 2018-07-06 | 2020-01-15 | 양일승 | Car engine managing method for reducing fine dust |
CN111321025A (en) * | 2020-02-26 | 2020-06-23 | 安徽正洁高新材料股份有限公司 | High-efficiency coal combustion-supporting additive and preparation method thereof |
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JP2009167301A (en) | 2009-07-30 |
ES2383623T3 (en) | 2012-06-22 |
TWI408222B (en) | 2013-09-11 |
JP4131748B1 (en) | 2008-08-13 |
CN101541930B (en) | 2013-02-13 |
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ATE553172T1 (en) | 2012-04-15 |
KR100979340B1 (en) | 2010-08-31 |
KR20090086149A (en) | 2009-08-11 |
WO2009090980A1 (en) | 2009-07-23 |
US20100050503A1 (en) | 2010-03-04 |
EP2107103A1 (en) | 2009-10-07 |
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EP2107103A4 (en) | 2010-06-09 |
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