EP3351610B1 - Additif pour combustible destiné à réduire les gaz à effet de serre, les oxydes d'azote et la matière particulaire - Google Patents

Additif pour combustible destiné à réduire les gaz à effet de serre, les oxydes d'azote et la matière particulaire Download PDF

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EP3351610B1
EP3351610B1 EP16846753.8A EP16846753A EP3351610B1 EP 3351610 B1 EP3351610 B1 EP 3351610B1 EP 16846753 A EP16846753 A EP 16846753A EP 3351610 B1 EP3351610 B1 EP 3351610B1
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fuel
heavy
fuel oil
weight
oil
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German (de)
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EP3351610A1 (fr
EP3351610A4 (fr
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Young Seo Lee
Myeong Jin Lee
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LEE, YOUNG SEO
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Definitions

  • the present disclosure relates to a fuel additive capable of reducing the generation of greenhouse gases, nitrogen oxides, and particulate matter and improving combustion efficiency by being added to a heavy fuel oil during combustion in an internal combustion engine or a boiler using a heavy fuel oil as fuel.
  • Korean Patent Registration Publication No. 10-0743826 discloses a fuel additive for a bituminous heavy fuel oil/water emulsion including 30 to 60% by weight of magnesium hydroxide having a particle size of 0.1 to 10 ⁇ m; 0.1 to 1% by weight of polycarboxylic acid and/or its salt; and the water of the remaining % by weight.
  • Korean Patent Registration Publication No. 10-1071204 discloses a fuel additive for a heavy fuel oil consisting of a composition including 25 to 55% by weight of an oil soluble metallic compound including any one of calcium, barium, manganese or iron, 15 to 25% by weight of alcohol, 10 to 20% by weight of hydrotreated light distillate, 5 to 15% by weight of kerosene, 5 to 15% by weight of mineral oil, and 2 to 8% by weight of non-ionic surfactant, in which the mineral oil is composed of one or more kinds selected from the group consisting of a hydrotreated heavy paraffinic distillate or a hydrotreated light paraffinic distillate, solvent-dewaxed heavy paraffinic distillate, solvent-dewaxed light paraffinic distillate, hydrotreated and dewaxed heavy paraffinic distillate, and hydrotreated and dewaxed light paraffinic distillate.
  • US2014/000156 relates to a fuel additive for heavy oil.
  • the present disclosure has been made under the background of the prior art, and an object of the present disclosure is to provide a method for reducing the generation of greenhouse gases, nitrogen oxides and particulate matter added to a heavy fuel oil during combustion in an internal combustion engine or a boiler using a heavy fuel oil as fuel, and to provide a fuel additive capable of improving combustion efficiency.
  • one aspect of the present disclosure provides a fuel additive for a heavy fuel oil in the form of a composition including an oil soluble metallic compound, an oxygen supplier, a dispersant, a lubricant, a non-ionic surfactant, and a detergent.
  • a fuel additive for a heavy fuel oil in the form of a composition including an oil soluble metallic compound, an oxygen supplier, a dispersant, a lubricant, a non-ionic surfactant, and a detergent.
  • the oil soluble metallic compound which is one of the components of the fuel additive for a heavy fuel oil according to the present disclosure, increases the reactivity with oxygen during the combustion of heavy fuel oil, which is fuel oil, accelerates the oxidation and promotes the combustion reaction of low combustibility components such as asphaltenes, and acts as a combustion promoter for suppressing generation of exhaust gas and dust.
  • the oil soluble metallic compound preferably includes a metal having a high combustion promoting reactivity, and at the same time has a property of being oil soluble in fuel-derived heavy oil. Examples of the metal having a high combustion promoting reactivity include calcium, barium, manganese or iron, etc.
  • the oil soluble metallic compound is composed of an active metal portion and an organic ligand in order to be well dissolved in fuel-derived heavy oil.
  • the oil soluble metallic compound include calcium acetylacetonate, calcium naphthenate, calcium oxlate, barium acetylacetonate, barium naphthenate, barium oxlate, manganese acetylacetonate, manganese naphthenate, manganese oxlate, iron acetylacetonate, iron naphthenate, iron oxlate, etc.
  • the oil soluble metallic compound may be a metal salt of a carboxylic acid or a metal salt of a sulfonic acid from a different viewpoint.
  • the oil soluble metallic compound in the present disclosure is an oil soluble metallic compound including calcium.
  • the calcium salt of the sulfonic acid is a calcium alkylbenzenesulfonate including a double alkylaryl group.
  • the alkyl group of the calcium alkylbenzenesulfonate is characterized by having 8 to 50 carbon atoms.
  • a specific example of the calcium alkylbenzenesulfonate is calcium dodecylbenzenesulfonate, which is a typical anionic surfactant.
  • the content of the oil soluble metallic compound is 20 to 25 wt% based on the total weight of the composition, considering the effect of minimizing dust generation and compatibility with other constituents.
  • the oxygen carrier which is one component of the fuel additive for a heavy fuel oil according to the present disclosure is preferably a compound having a low boiling point.
  • the low boiling point compound can contribute to complete combustion by increasing the combustion reaction surface area by the vaporization phenomenon inside a burner spray droplet.
  • the low boiling point compound used as an oxygen carrier in the present disclosure is dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, methylethyl carbonate, methylpropyl carbonate, or ethypropyl carbonate.
  • the content of the oxygen carrier is 30 to 35% by weight based on the total weight of the composition, considering the effect of minimizing dust generation and compatibility with other components.
  • the dispersant which is one component of the fuel additive for a heavy fuel oil according to the present disclosure, plays as a role in preventing the formation of sludge, lowering the flash point of the heavy fuel oil, and reducing the kinematic viscosity and surface tension.
  • the viscosity and the surface tension of the heavy fuel oil are reduced, the particle diameter of the fuel becomes atomized and homogenized at the time of injection from the nozzle, and it is possible to lower the temperature of the exhaust gas of the internal combustion engine by the rapid combustion and the low temperature explosion at the time of combustion.
  • the dispersant is a hydrotreated light distillate.
  • Hydrotreated is a treatment method of adding hydrogen to oil, etc.
  • the light distillate refers to a light hydrocarbon which is distilled first when the crude oil is distilled.
  • the hydrotreated light distillate has a boiling point of usually 150 to 300°C, but is not limited thereto.
  • the hydrotreated light distillate which can be used in the present disclosure includes products such as CAS Registration Nos. 64742-47-8 and 68921-07-3, but is not limited thereto.
  • the content of the hydrotreated light distillate is 15 to 20% by weight based on the total weight of the composition, considering the effect of reducing the flash point and the kinematic viscosity, minimizing the generation of dust and residual carbon powder and the compatibility with other components.
  • the lubricant which is one component of the fuel additive for a heavy fuel oil according to the present disclosure, plays a role in maintaining the shape of sludge redispersed in the form of microparticles and suppressing the occurrence of friction in an internal combustion engine.
  • the lubricant is preferably a paraffinic oil, more preferably modified by hydrotreating or dewaxing treatment.
  • the paraffinic oil modified by the hydrotreating or dewaxing treatment may be composed of at least one selected from the group consisting of a hydrotreated heavy paraffinic distillate ( CAS Registration No. 64742-54-7 ), a hydrotreated light paraffinic distillate ( CAS Registration No.
  • a solvent-dewaxed heavy paraffinic distillate CAS Registration No. 64742-65-0
  • a solvent-dewaxed light paraffinic distillate CAS Registration No. 64742-56-9
  • a hydrotreated and dewaxed heavy paraffinic distillate CAS Registration No. 91995-39-0
  • a hydrotreated and dewaxed light paraffinic distillate CAS Registration No. 91995-40-3
  • the content of the lubricant is 3 to 7% by weight based on the total weight of the composition, considering the effect of reducing the flash point and the kinematic viscosity, minimizing the generation of dust and residual carbon powder and the compatibility with other components.
  • the non-ionic surfactant which is one component of the fuel additive for a heavy fuel oil according to the present disclosure, plays a role in preventing the formation of sludge and redispersing the generated sludge into a microparticle.
  • the non-ionic surfactant exhibits a repulsion due to steric hindrance to form a stable dispersion system.
  • an ionic material such as an oil soluble metallic compound
  • the non-ionic surfactant used in the present disclosure is not greatly limited in its kinds such as ester base, ether base, fatty acid amide base, aliphatic amine derivative, and the like.
  • ester-based non-ionic surfactant include sorbitan esters of fatty acids, pentaerythritol esters of fatty acids, propyleneglycol monoesters of fatty acids, glycerin monoesters of fatty acids, polyethyleneglycol sorbitan esters of fatty acids, polyethyleneglycol sorbitol esters of fatty acids, and polyethyleneglycol esters of fatty acids, and the like.
  • Examples of the ether-based non-ionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkylpolyglycosides, and the like.
  • Examples of the fatty acid amide-based non-ionic surfactant include fatty acid dialkanolamides, fatty acid monoalkanolamides, polyoxyethylene fatty acid amides, and the like.
  • Examples of the aliphatic amine derivative non-ionic surfactant include polyoxyethylene alkylamine, and the like.
  • the non-ionic surfactant used in the present disclosure is composed of at least one selected from the group consisting of sorbitan esters of fatty acids, polyethyleneglycol esters of fatty acids, or polyethylene glycol sorbitan esters of fatty acids.
  • Examples of sorbitan esters of fatty acids include sorbitan monooleate, sorbitan monolaurate, and the like.
  • Examples of the polyethyleneglycol sorbitan esters of fatty acids include polyethylene glycol sorbitan monooleate, and the like.
  • Examples of the polyethyleneglycol esters of fatty acids include polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol monoricinoleate, polyethylene glycol monostearate, and the like.
  • the content of the non-ionic surfactant is preferably 8 to 15% by weight based on the total weight of the composition, considering the effect of reducing the flash point and the kinematic viscosity, minimizing the generation of dust and residual carbon powder and the compatibility with other components.
  • the detergent which is one component of the fuel additive for a heavy fuel oil according to the present disclosure, plays a role in decomposing the secondary oxide and the combustion products to reduce the formation of precipitates on the surface of the metal parts surface.
  • the detergent may be composed of at least one selected from the group consisting of alkaline metal salts of a known sulfonate, alkaline earth metal salts of sulfonates, alkaline metal salts of phenates, alkaline earth metal salts of phenates, alkaline metal salts of salicylates, alkaline earth metal salts of salicylates, alkaline metal salts of naphthenate, or alkaline earth metal salts of naphthenate.
  • the alkaline metal or alkaline earth metal is preferably selected from calcium, magnesium, sodium, or barium.
  • the metal salt-type detergent may include a metal in a stoichiometric amount or in excess thereof. In the latter case, it is treated as an overbased detergent.
  • the overbased detergent is a metal salt that dissolves in oil and appears as a micelle consisting of an insoluble metal salt trapped in a suspension in a fuel oil composition described later.
  • the overbased characteristic of the detergent is characterized by total base number (TBN), measured in accordance with ASTM D2896 standard, and is expressed in mg of KOH per gram.
  • TBN total base number
  • the overbased detergent itself typically has a TBN value of about 150 or more, or 250 or 450 or more. In the present disclosure, it is preferable that the detergent is an overbased detergent in consideration of the synergistic effect with other components.
  • the TBN of the overbased detergent is preferably 200 or more, more preferably 300 or more.
  • the overbasing process is well known in the pertinent art and typically involves reacting an acidic material with a reaction mixture including an organic acid or metal salt thereof, or a metal compound.
  • the acidic material may be a gas such as carbon dioxide or sulfur dioxide, or it may be boric acid.
  • a method for preparing an overbased alkaline metal sulfonate and phenate is described in U.S. Patent No. 4,839,094 .
  • a suitable method for an overbased sodium sulfonate is described in EP-A-235929 .
  • a method for preparing an overbased salicylate is described in U.S. Patent No. 5,451,331 .
  • overbased detergents include T106 (Overbased Heavy alkyl benzene synthetic calcium sulfonate of Anneng Chemical Co., Ltd. ( CAS registration no. 61789-86-4 )), CALCINATETM C-300CS of Chemtura Corporation, OLOA 246S (Sulfonic acids, petroleum, calcium salts, overbased ( CAS Registration No. 68783-96-0 )) of Chevron Chemical Company, and the like.
  • the overbased sulfonate-based detergent of CAS Registration No. 68783-96-0 has the structure of the following Formula 1
  • the overbased sulfonate-based detergent of CAS Registration No. 115733-10-3 has the structure of the following Formula 2.
  • the content thereof is 7 to 15% by weight based on the total weight of the composition, considering the effect of improving combustion of the detergent, reducing NOx, minimizing the generation of dust and residual carbon powder and the compatibility with other components.
  • another aspect of the present disclosure relates to a fuel oil based on a heavy fuel oil, in which the fuel oil based on a heavy fuel oil according to the present disclosure includes a heavy fuel oil and the above-described fuel additives for a heavy fuel oil.
  • the heavy fuel oil is not limited in its kind, and may be a heavy oil A, a heavy oil B, a heavy oil C (or bunker C oil), or a mixed heavy oil thereof.
  • the content of the fuel additive for a heavy fuel oil in the fuel oil is not limited to a great extent.
  • the fuel additive of the present disclosure is very useful for a large boiler using a heavy fuel oil as fuel, in particular, a large diesel engine.
  • the applicant of the present disclosure attempted to reduce the fuel cost by injecting a predetermined fuel additive (including an oil-soluble calcium-based organometallic compound as one component) into a heavy fuel oil for ships.
  • a method of reducing a fuel cost by injecting a predetermined amount of a fuel additive (including an oil-soluble calcium-based organometallic compound as one component) (0.025% of a fuel amount used) was tried.
  • a two-stroke large diesel engine installed in the land-based power plant was an experiment object.
  • the experimental engine load was divided into low, medium and high load (50, 75, 100%).
  • the engine performance output, fuel consumption rate, maximum combustion pressure (P-max), exhaust temperature) before and after the injection of fuel additives was compared and analyzed.
  • Table 1 exihibits the specifications of the experimental engine used in this study.
  • the equipment to be applied for the performance experiment is Diesel Engine Generator equipment manufactured and installed by Doosan Engine Co., Ltd, and is a 40MW generator.
  • Table 2 exihibits the properties of the fuels used in this study and exihibits the fuel properties of heavy fuel oil after injecting fuel additives at 0.025% ratio of heavy fuel oil and the fuel properties of heavy fuel oil before injecting them into a heavy fuel oil for ships.
  • the fuel additive an additive including an oil-soluble calcium-based organometallic compound was used. To analyze the fuel composition of each fuel, three samples were collected during the experiment to analyze the exact composition of the fuel.
  • the fuel additive injection system installed a dosing pump that can automatically supply a certain amount around the control tank, and the supply position is connected to a supply piping so that it can be supplied to the top of the fuel control tank.
  • the engine output was measured in a local integrated watt-hour meter and a control room meter, and the fuel consumption amount was referred to an on-site mass flowmeter reading installed on the fuel oil supply line side.
  • Table 3 exihibits the dosing pump and mass flowmeter specifications. In calculating the engine output and fuel consumption rate, each item on the performance was calculated by applying the calibration curve and formula given by the manufacturer.
  • FIG. 1 is a schematic diagram of an experimental apparatus for an engine used in this study. [Table 3] Item Description Dosing pump CMG Techwin, AX1-12 model, 110 ml/min Mass flowmeter Endress Hauser, IP67/NEMA/TYPE4X model
  • the engine output was measured by dividing them into three stages of low, medium and high load (50, 75, 100%). At the low load of 50% of the engine load, the average value measured 4 times is exihibited. At the medium load of 75% and the high load of 100% of the engine load, the average value measured 7 times is exihibited. Table 4 exihibitsthe rate of increase and decrease of the output at each load, and FIG. 2 illustrates the results thereof in the form of a graph. At a low load of 50%, the output decreased by about 2.1%, but increased by about 1.6% and 0.4% at 75% of medium load and 100% of high load, respectively. These results indicate that the output is improved by completely combusting the unburned matter with the fuel additive effect at a load of 75% or more.
  • This engine output value is a value obtained by calibrating the measured output value with the design Gen power factor value.
  • Table 5 and FIG. 3 exhibit the results of the fuel consumption rate.
  • the average value measured 4 times is exihibited.
  • the medium load of 75% and the high load of 100% of the engine load the average value measured 7 times is exihibited.
  • the fuel consumption rate decreased by about 2.2%, and decreased by about 0.7% and 0.8% of medium and high loads. It is determined that these results are produced by combustion promotion. That is, it was confirmed that the fuel efficiency was improved at full load by injecting the fuel additive into the heavy fuel oil. In particular, the fuel consumption reduction rate was higher at low load than at medium and high load regions.
  • Table 6 and FIG. 4 exhibit the results of the maximum combustion pressure of the engine. Each value was measured after all cylinders 12 cylinders were measured, and the average value was exihibited. The maximum combustion pressure increased about 3.0% at low load and increased about 6.6% and 0.9% at medium and high load, respectively. That is, it was confirmed that the maximum combustion pressure was increased at full load by injecting the fuel additive into the heavy fuel oil for ships. In particular, it exhibits a large increase rate in medium load of 75%, which is the commercial load of the engine. As exihibitedin Table 2, it is analyzed that engine combustion is promoted actively by the action of oxygen included in the fuel additive, thereby improving combustion.
  • Table 7 and FIG. 5 exhibit the post-combustion temperature of the engine at each load. Each value was measured after all cylinders 12 cylinders were measured, and the average value was exhibited. At the low load, the exhaust temperature decreased by about 2.7%, and at medium and high loads, it decreased by about 2.4% and 0.6%. That is, it was confirmed that the exhaust temperature decreases at full load by injecting the fuel additive into the heavy fuel oil. It is determined that the asphalt and sludge included in the heavy fuel oil are well dispersed by the dispersant included in the fuel additive, thereby producing the fuel atomization and homogenization effect of fuel during the fuel injection so as to be stable combustion.
  • the fuel cost can be reduced by 2% or more at the low load (50%) by injecting the predetermined fuel additive including the oil soluble calcium-based organometallic compound into a heavy fuel oil for ships which is currently used in the two-stroke high-power large diesel engine.
  • the maximum combustion pressure increases, whereas the exhaust temperature is lowered.
  • the engine performance is improved. Accordingly, it is possible to reduce fuel costs by injecting a fuel additive into a two-stroke large diesel engine which uses a heavy fuel oil for ships.
  • Tables 8 and 9 exhibit the emission changes of nitrogen oxide (NOx) according to the addition of the fuel additive and Table 9 exhibits the emission change of particulate matter (PM) according to the addition of the fuel additive.
  • NOx nitrogen oxide
  • PM particulate matter

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Claims (4)

  1. Additif de carburant pour un fioul lourd sous forme de composition, l'additif de carburant comprenant :
    20 à 25% en poids d'un composé métallique soluble dans l'huile ; 30 à 35% en poids d'un véhicule oxygéné ; 15 à 20% en poids d'un dispersant ; 3 à 7% en poids d'un lubrifiant; 8 à 15% en poids d'un agent tensioactif non ionique ; et 7 à 15% en poids d'un détergent surbasique à base de sulfonate, par rapport au poids total de la composition,
    le composé métallique soluble dans l'huile étant un alkylbenzènesulfonate de calcium et le groupe alkyle ayant 8 à 50 atomes de carbone,
    le véhicule oxygéné étant composé d'au moins un élément choisi dans le groupe constitué par le carbonate de diméthyle, le carbonate de diéthyle, le carbonate de dipropyle, le carbonate de diiosopropyle, carbonate de dibutyle, carbonate de dipentyle, carbonate de méthyléthyle, carbonate de méthylpropyle et carbonate d'éthylpropyle,
    le dispersant étant un distillat léger hydrotraité,
    le lubrifiant étant composé d'au moins un élément choisi dans le groupe constitué par un distillat paraffinique lourd hydrotraité, un distillat paraffinique léger hydrotraité, un distillat paraffinique lourd déparaffiné au solvant, un distillat paraffinique léger déparaffiné au solvant, un distillat paraffinique lourd hydrotraité et déparaffiné ou un distillat paraffinique léger hydrotraité et déparaffiné,
    l'agent tensioactif non ionique étant composé d'au moins un élément choisi dans le groupe constitué par les esters de sorbitane d'acides gras, les esters de polyéthylèneglycol d'acides gras et les esters de sorbitane de polyéthylèneglycol d'acides gras,
    le détergent surbasique à base de sulfonate étant composé d'un composé du numéro d'enregistrement CAS. 68783-96-0 ou un composé du numéro d'enregistrement CAS 115733-10-3.
  2. Additif de carburant pour un fioul lourd selon la revendication 1, l'agent tensioactif non ionique étant composé d'au moins un élément choisi dans le groupe constitué par le monooléate de sorbitane, le monolaurate de sorbitane ou le monooléate de sorbitane polyéthylèneglycol.
  3. Fioul comprenant un fioul lourd et l'additif pour un fioul lourd selon l'une des revendications 1 à 2.
  4. Fioul selon la revendication 3, dans lequel la teneur en additif pour un fioul lourd dans le fioul est de 0,001 à 0,5 partie en poids pour 100 parties en poids du fioul lourd.
EP16846753.8A 2015-09-17 2016-08-11 Additif pour combustible destiné à réduire les gaz à effet de serre, les oxydes d'azote et la matière particulaire Active EP3351610B1 (fr)

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DE3676384D1 (de) * 1985-08-13 1991-02-07 Exxon Chemical Patents Inc Ueberbasische zusaetze.
GB8621343D0 (en) * 1986-09-04 1986-10-15 Exxon Chemical Patents Inc Overbased alkali metal additives
IT1293180B1 (it) * 1996-06-11 1999-02-16 Globe S P A ADDITIVO PER GASOLIO DI AUTOTRAZIONE IN GRADO DI MIGLIORARE LA QUALITà DEI GAS DI SCARICO NEI MOTORI A CICLO DIESEL.
DE19643832A1 (de) * 1996-10-30 1998-05-07 Clariant Gmbh Schwere Öle mit verbesserten Eigenschaften und ein Additiv dafür
WO1998026028A1 (fr) * 1996-12-09 1998-06-18 Orr William C Compositions de carburant caracterisees par une stabilite amelioree dudit carburant
KR100569899B1 (ko) 2003-10-20 2006-04-10 현대자동차주식회사 디젤 엔진의 디메틸에테르 공급장치
US9481841B2 (en) * 2004-12-09 2016-11-01 The Lubrizol Corporation Process of preparation of an additive and its use
GB0700534D0 (en) * 2007-01-11 2007-02-21 Innospec Ltd Composition
JP5638256B2 (ja) * 2010-02-09 2014-12-10 出光興産株式会社 潤滑油組成物
KR101071204B1 (ko) 2011-03-08 2011-10-10 이영서 중유용 연료첨가제 및 이를 포함하는 연료유
CN104593106B (zh) * 2015-01-22 2015-08-05 杨长江 一种高清洁柴油添加剂及制备方法
CN104862021A (zh) * 2015-04-20 2015-08-26 刘敏 一种复合柴油及其制备方法

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