WO2024101498A1 - Fuel additive composition for bio-heavy oil, and use thereof - Google Patents

Fuel additive composition for bio-heavy oil, and use thereof Download PDF

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WO2024101498A1
WO2024101498A1 PCT/KR2022/017909 KR2022017909W WO2024101498A1 WO 2024101498 A1 WO2024101498 A1 WO 2024101498A1 KR 2022017909 W KR2022017909 W KR 2022017909W WO 2024101498 A1 WO2024101498 A1 WO 2024101498A1
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heavy oil
weight
bio
oil
fuel
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이영서
이명진
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  • the present invention relates to a fuel additive composition, etc., and more specifically, to a fuel additive composition for bio heavy oil that can be added to bio heavy oil to improve the lubricity and storage stability of bio heavy oil and its use.
  • Bio-heavy oil is a biofuel manufactured by reacting unutilized resources such as biodiesel process by-products (pitch), discarded animal fat, discarded vegetable oil, and palm by-products with methanol or ethanol, and is a petroleum-based heavy oil (e.g. For example, it has similar characteristics to bunker C oil, so it can be mixed with petroleum-based heavy oil or is recently attracting attention as an eco-friendly fuel that can 100% replace petroleum-based heavy oil.
  • bio heavy oil mainly uses low-quality animal and vegetable oil as a raw material, it is known to be of lower quality than biodiesel, but has a high calorific value, so it is suitable for use for power generation.
  • bio-heavy oil is a product manufactured by mixing various animal and vegetable oils, fatty acid methyl esters, fatty acid ethyl esters, and their by-products, so there is a problem of lower quality reliability compared to heavy oil manufactured from petroleum raw materials.
  • various by-products such as palm oil oil, animal and vegetable oil, etc. are used as raw materials, so the physical properties change depending on the composition of the raw material, which results in quality standards.
  • the right mix of raw materials is important.
  • bio-heavy oil has a very low sulfur and nitrogen content compared to petroleum-based heavy oil (for example, bunker C oil), so it has the effect of reducing harmful emissions such as sulfur oxides (SOx) and nitrogen oxides (NOx). Although it is large, it has a high acid number and low viscosity [Jang Yun-jeong et al., "Study on the quality characteristics of bio heavy oil for power generation as an alternative fuel to heavy oil”: Journal of Korean Oil Chem.SOC., Vol.31, No.4, December , 2014, 562-571].
  • bio-heavy oil may inhibit the formation of a lubricant film due to its acidic components, and reduced lubricity can cause friction and wear in fuel supply systems such as fuel pumps, flow pumps, and injectors, resulting in serious damage.
  • the main components of petroleum-based heavy oil for example, Bunker C oil
  • the main components of bio-heavy oil are paraffin, naphthene, and olefin aromatics
  • the main components of bio-heavy oil are triglyceride fatty acids, fatty acid methyl esters, As fatty acid ethyl ester, etc.
  • bio-heavy oil has more unsaturated double bonds and contains a large amount of oxygen compared to petroleum-based heavy oil (for example, Bunker C oil), so it has low oxidation stability and high reactivity.
  • bio-heavy oil can easily be mixed with atmospheric moisture during the storage process, and the moisture content may increase, reducing storage stability.
  • bio-heavy oil is a product produced by mixing vegetable or animal oils derived from various regions or raw materials, fatty acid esters, and by-products, so sludge is generated depending on the composition of the components. Since it is easy and this can cause problems such as clogging of fuel injection nozzles, it is necessary to secure storage stability by dispersing or dissolving the sludge material in a colloidal state.
  • bio-heavy oil is generally used by mixing with petroleum-based heavy oil (e.g., Bunker C oil). Bio-heavy oil and petroleum-based heavy oil (e.g., Bunker C oil) There is a problem with poor compatibility because the main ingredients are different.
  • Republic of Korea Patent Publication No. 10-1836946 contains 20 to 25% by weight of calcium alkylbenzenesulfonate based on the total weight; 30 to 35% by weight of one or more oxygen supply agents selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, or ethyl propyl carbonate.
  • one or more oxygen supply agents selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, or ethyl propyl carbonate.
  • a fuel additive for heavy oil in the form of a composition comprising 7 to 15% by weight of an overbased calcium salt of benzenesulfonic acid to which a C14-C24 branched or linear alkyl group is bonded is disclosed.
  • the fuel additive disclosed in the prior patent is added to petroleum-based heavy oil to improve combustion efficiency, but there are limitations in its application to bio-heavy oil, which shows significant differences in major components and physical properties from petroleum-based heavy oil. .
  • the present invention was derived from the conventional technical background, and the purpose of the present invention is to improve the lubricity and storage stability of bio-heavy oil by adding it to bio-heavy oil, or to improve the lubricity and storage stability of bio-heavy oil and petroleum oil.
  • the aim is to provide a fuel additive composition that can improve the compatibility of heavy oil. Additionally, the purpose of the present invention is to provide a use of a fuel additive composition for bio heavy oil.
  • the inventor of the present invention manufactured a fuel additive composition consisting of a combination of various ingredients, and added the prepared fuel additive composition to bio-heavy oil or a mixed oil of bio-heavy oil and petroleum-based heavy oil. Afterwards, as a result of measuring the lubricity and storage stability of bio-heavy oil, the lubricity and storage stability of bio-heavy oil were significantly improved when the fuel additive composition consisted of a combination of specific ingredients. It was confirmed that the compatibility between bio-heavy oil and petroleum-based heavy oil was greatly improved, and the present invention was completed.
  • an example of the present invention is a mono-C 10-14 -alkyl derivative of benzene (Benzene, mono-C 10-14 -alkyl derivatives; CAS registration number 68442-69-3) based on the total weight.
  • the fuel additive composition for bio-heavy oil preferably contains mono-C 10- of benzene based on the total weight.
  • 14 -alkyl derivatives (Benzene, mono-C 10-14 -alkyl derivatives; CAS registration number 68442-69-3) 25 ⁇ 30% by weight, Hydrotreated light distillates (CAS registration number 64742-47- 8) 20-30% by weight, pentaerythritol tetraoleate (CAS registration number 19321-40-5) 10-20% by weight, branched, cyclic and straight-chain hydrocarbon distillate with 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 10-15% by weight and C 14-24 -branched and straight-chain alkyl derivatives of benzenesulfonic acid overbased calcium salts ( Benzene, mono-C 10-14 -alkyl derivatives; CAS registration number 68442-69-3) 25
  • Benzene, mono-C 10-14 -alkyl derivatives (CAS registration number 68442-69-3 ) and hydrotreated light distillates (CAS registration number 64742) -47-8) are mainly components involved in suppressing sludge formation and improving dispersibility and storage stability of bio heavy oil.
  • pentaerythritol tetraoleate (CAS registration number 19321-40-5) and branched, cyclic and straight-chain hydrocarbon distillates having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and Linear hydrocarbons - Distillates; CAS registration number 848301-69-9) are components mainly involved in improving the lubricity of bio heavy oil.
  • Benzenesulfonic acid C 14-24 -branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3
  • the fuel additive composition for bio-heavy oil according to an example of the present invention greatly improves the lubricity and storage stability of bio-heavy oil by having the components exert their main functions and at the same time exert a synergistic effect through interaction.
  • the compatibility of bio-heavy oil and petroleum-based heavy oil can be greatly improved.
  • an example of the present invention provides fuel oil containing bio heavy oil and the above-described fuel additive composition for bio heavy oil.
  • the content of the fuel additive composition in the fuel oil according to an example of the present invention is not greatly limited, and considering the effect of improving the lubricity and storage stability of bio-heavy oil, it is 0.01 to 0.01 parts by weight per 100 parts by weight of bio-heavy oil. It is preferably 0.2 parts by weight, and more preferably 0.015 to 0.1 parts by weight per 100 parts by weight of bio heavy oil.
  • another example of the present invention provides fuel oil containing petroleum-based heavy oil, bio heavy oil, and the above-described fuel additive composition for bio heavy oil.
  • the petroleum-based heavy oil is a dark brown viscous oil obtained after extracting gasoline, kerosene, diesel, etc. from crude oil. Petroleum-based heavy oil used as a fuel is called bunker oil.
  • the types of petroleum heavy oil are not greatly limited as long as they are used as fuel for ships, boilers, and power generation, such as Bunker A oil, Bunker B oil, and Bunker C oil. No.
  • the mixing weight ratio of petroleum heavy oil to bio heavy oil in the fuel oil according to another example of the present invention is not greatly limited, and may be, for example, 2:8 to 8:2, and 3:7 to 7:3. .
  • the content of the fuel additive composition in the fuel oil according to another example of the present invention is not greatly limited, and considering the effect of improving the miscibility of petroleum heavy oil and bio heavy oil, the total amount of petroleum heavy oil and bio heavy oil is 0.01 per 100 parts by weight. It is preferably from 0.2 parts by weight, and more preferably from 0.015 to 0.1 parts by weight per 100 parts by weight of the total of petroleum heavy oil and bio heavy oil.
  • the fuel additive composition for bio-heavy oil according to the present invention significantly improves the lubricity and storage stability of bio-heavy oil, or greatly improves the compatibility between bio-heavy oil and petroleum-based heavy oil. It can be improved. Therefore, by using the fuel additive composition for bio-heavy oil according to the present invention, problems arising from bio-heavy oil can be solved and the scope of application of bio-heavy oil can be greatly expanded.
  • Benzene, mono- C10-14 -alkyl derivatives (CAS registration number 68442-69-3) 28 parts by weight, Hydrotreated light distillates (CAS registration number) 64742-47-8) 23 parts by weight, pentaerythritol tetraoleate (CAS registration number 19321-40-5) 20 parts by weight, branched, cyclic and straight-chain hydrocarbon distillate having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 14 parts by weight and C 14-24 -branched and straight chain alkyl derivatives of benzenesulfonic acid , C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3) were mixed uniformly to prepare a fuel additive composition.
  • Benzene, mono- C10-14 -alkyl derivatives (CAS registration number 68442-69-3), Hydrotreated light distillates (CAS registration number) 64742-47-8) 30 parts by weight, pentaerythritol tetraoleate (CAS registration number 19321-40-5) 15 parts by weight, branched, cyclic and straight-chain hydrocarbon distillate having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 10 parts by weight and C 14-24 -branched and linear alkyl derivatives of benzenesulfonic acid , C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3) were mixed uniformly to prepare a fuel additive composition.
  • Hydrotreated light distillates 51 parts by weight, branched, cyclic and straight-chain hydrocarbon distillates having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 34 parts by weight C 14-24 -branched and linear alkyl derivatives of benzenesulfonic acid , calcium salts, overbased; CAS registration number 115733-10-3) was mixed uniformly to prepare a fuel additive composition.
  • Hydrotreated light distillates (CAS registration number 64742-47-8) 51 parts by weight, Pentaerythritol tetraoleate (CAS registration number 19321-40-5) 34 parts by weight and benzenesulfonic acid 15 parts by weight of C 14-24 -branched and linear alkyl derivatives, calcium salts, overbased (CAS registration number 115733-10-3) uniformly
  • a fuel additive composition was prepared by mixing.
  • Benzene, mono- C10-14 -alkyl derivatives (CAS registration number 68442-69-3), Hydrotreated light distillates (CAS registration number) 64742-47-8) 37 parts by weight and C 14-24 -branched and linear alkyl derivatives of benzenesulfonic acid (Benzenesulfonic acid, C 14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS registered) Number 115733-10-3)
  • a fuel additive composition was prepared by uniformly mixing 15 parts by weight.
  • bio heavy oil consisting of 40% by weight of palm acid oil, 15% by weight of animal oil, 20% by weight of fatty acid methyl ester, and 25% by weight of biodiesel pitch. did.
  • the fuel additive compositions prepared in Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 3 were added to the prepared bio heavy oil in an amount of 200 ppm and mixed to prepare fuel oil.
  • the lubricity of fuel oil was measured using the HFRR (High-Frequency Reciprocating Rig) test method included in the ASTM D6079 standard test method.
  • the HFRR test method is a method of evaluating the lubricity of diesel fuel. Measured values are provided in micrometers ( ⁇ m), and the lower the value, the better the lubricity. Table 1 below summarizes the lubricity measurement values of bio heavy oil-based fuel oil.
  • the storage stability of fuel oil was measured using the spot test, which is included in the ASTM D4740 standard test method.
  • the Spot Test is used to measure the stability of fuel oil itself, such as sludge production in fuel oil, or to measure the miscibility of different fuels, and the measured values are spot ratings 1, 2, 3, 4, and 5. It is provided in five grades, and the closer it is to a spot rating of 1, the better the storage stability or miscibility, and the closer it is to a spot rating of 5, the worse the storage stability or miscibility is.
  • Table 2 summarizes the judgment criteria according to spot rating.
  • spot rating Criteria One Homogeneous spot (no inner ring) 2 Faint or poorly defined inner ring 3 Well-defined thin inner ring, only slightly darker than the background 4 / Well-defined inner ring, thicker than the ring in reference spot No. 3 and somewhat darker than the background 5 Very dark solid or nearly solid area in the center. The color of the center is darker than the background. The central area is much darker than the background
  • Table 3 summarizes the storage stability measurements of bioheavy oil-based fuel oil.
  • Fuel oil sample classification Classification of fuel additive compositions added to fuel oil spot rating fuel oil 1 Manufacturing Example 1 One fuel oil 2 Production example 2 One fuel oil 3 Production example 3 One fuel oil 4 Comparative Manufacturing Example 1 3 fuel oil 5 Comparative Manufacturing Example 2 3 fuel oil 6 Comparative Manufacturing Example 3 One
  • Bio heavy oil consisting of 40% by weight of palm acid oil, 15% by weight of animal oil, 20% by weight of fatty acid methyl ester, and 25% by weight of biodiesel pitch. did.
  • Mixed heavy oil was prepared by mixing the prepared bio heavy oil and bunker C oil at a weight ratio of 1:1. Thereafter, the fuel additive compositions prepared in Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 3 were added to the mixed heavy oil in an amount of 200 ppm and mixed to prepare mixed fuel oil.
  • the compatibility of the mixed fuel oil was measured using the Spot Test included in the ASTM D4740 standard test method, and the compatibility of Bunker C oil and bio heavy oil-based mixed fuel oil is measured in Table 4 below. The values have been organized.

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Abstract

One embodiment of the present invention provides a fuel additive composition for bio-heavy oil, comprising: mono-C10-14-alkyl derivatives of benzene (benzene, mono-C10-14-alkyl derivatives); hydrotreated light distillates; pentaerythritol tetraoleate; C18-C50 branched, cyclic and linear hydrocarbons - distillates; and overbased calcium salts of C14-24-branched and linear alkyl derivatives of benzenesulfonic acid (benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased). The fuel additive composition for bio-heavy oil, according to the present invention, can greatly improve the lubricity and storage stability of bio-heavy oil or greatly enhance the compatibility of bio-heavy oil and petroleum-based heavy oil.

Description

바이오중유용 연료첨가제 조성물 및 이의 용도Fuel additive composition for bio heavy oil and its uses
본 발명은 연료첨가제 조성물 등에 관한 것으로서, 더 상세하게는 바이오중유에 첨가되어 바이오중유의 윤활성 및 저장 안정성 등을 향상시킬 수 있는 바이오중유용 연료첨가제 조성물 및 이의 용도에 관한 것이다.The present invention relates to a fuel additive composition, etc., and more specifically, to a fuel additive composition for bio heavy oil that can be added to bio heavy oil to improve the lubricity and storage stability of bio heavy oil and its use.
바이오중유(Bio-heavy oil)는 바이오디젤 공정 부산물(피치), 버려지는 동물성 유지, 버려지는 식물성 유지, 팜 부산물 등 미활용 자원을 메탄올 또는 에탄올과 반응시켜 제조한 바이오연료로서, 석유계 중유(예를 들어, 벙커C유)와 특성이 유사하여 석유계 중유와 혼합하여 사용하거나 최근 석유계 중유를 100% 대체할 수 있는 친환경 연료로 주목받고 있다. 또한, 바이오중유는 품질이 낮은 동·식물성 유지를 원료로 주로 사용하기 때문에 바이오디젤보다는 품질이 낮지만 발열량이 높아 발전용으로 사용하기에 무리가 없는 것으로 알려져 있다.Bio-heavy oil is a biofuel manufactured by reacting unutilized resources such as biodiesel process by-products (pitch), discarded animal fat, discarded vegetable oil, and palm by-products with methanol or ethanol, and is a petroleum-based heavy oil (e.g. For example, it has similar characteristics to bunker C oil, so it can be mixed with petroleum-based heavy oil or is recently attracting attention as an eco-friendly fuel that can 100% replace petroleum-based heavy oil. In addition, since bio heavy oil mainly uses low-quality animal and vegetable oil as a raw material, it is known to be of lower quality than biodiesel, but has a high calorific value, so it is suitable for use for power generation.
한편, 바이오중유(Bio-heavy oil)는 다양한 동·식물성 유지, 지방산 메틸에스테르, 지방산 에틸에스테르 및 그 부산물을 혼합하여 제조된 제품이기 때문에 석유 원료로부터 제조된 중유에 비해 품질의 신뢰성이 떨어지는 문제가 있다. 예를 들어, 바이오중유(Bio-heavy oil)는 제조 과정에서 팜유 계열의 유지, 동·식물성 유지 등과 같이 다양한 부산물을 원료를 사용하기 때문에 원료의 조성에 따라 물성이 변하게 되고, 이로 인해 품질기준에 맞는 원료의 혼합이 중요하다. 또한, 바이오중유(Bio-heavy oil)는 석유계 중유(예를 들어, 벙커C유)에 비해 황분 및 질소 함량이 매우 낮아 황산화물(SOx)과 질소산화물(NOx) 등 유해 배출가스 저감 효과가 크지만, 전산가(Acid number)가 높고 점도는 낮다[장윤정 외, "중유 대체 연료로서 발전용 바이오 중유의 품질 특성 연구" : Journal of Korean Oil Chem.SOC., Vol.31, No.4, December, 2014, 562~571]. 따라서, 바이오중유(Bio-heavy oil)는 산성 성분에 의해 윤활막 형성이 저해될 수 있고, 윤활성 저하는 연료펌프, 유량펌프, 인젝터 등의 연료공급시스템에서 마찰 및 마모를 유발하여 심각한 피해를 초래할 수 있다. 또한, 석유계 중유(예를 들어, 벙커C유)는 주요 성분이 파라핀, 나프텐, 올레핀 방향족 등이지만 바이오중유(Bio-heavy oil)는 주요 성분이 트리글리세라이드(triglyceride) 지방산, 지방산 메틸에스테르, 지방산 에틸에스테르 등으로서, 바이오중유(Bio-heavy oil)는 석유계 중유(예를 들어, 벙커C유)에 비해 불포화 이중결합이 많고 산소를 다량 함유하고 있으므로 산화안정성이 낮고 반응성이 높다. 이로 인해 바이오중유(Bio-heavy oil)는 저장 과정에서 대기 중의 수분이 쉽게 혼입될 수 있고, 수분 함량이 증가하여 저장 안정성이 저하될 수 있다. 또한, 바이오중유(Bio-heavy oil)는 다양한 지역이나 원료들에서 유래되는 식물성 또는 동물성 유지와 지방산 에스테르 및 부산물 등을 혼합하여 생산한 제품이기 때문에 구성성분들의 조성에 의해 슬러지(Sludge)가 생성되기 쉽고 그로 인해 연료 분사 노즐의 막힘 현상 등의 문제가 발생할 수 있으므로 슬러지 물질을 콜로이드 상태로 분산 또는 용해시켜 저장 안정성을 확보할 필요가 있다. 또한, 바이오중유(Bio-heavy oil)는 일반적으로 석유계 중유(예를 들어, 벙커C유)와 혼합되어 사용되는데, 바이오중유(Bio-heavy oil)와 석유계 중유(예를 들어, 벙커C유)는 주요 성분들이 상이하여 혼화성(Compatibility)이 떨어지는 문제가 있다.Meanwhile, bio-heavy oil is a product manufactured by mixing various animal and vegetable oils, fatty acid methyl esters, fatty acid ethyl esters, and their by-products, so there is a problem of lower quality reliability compared to heavy oil manufactured from petroleum raw materials. there is. For example, during the manufacturing process of bio-heavy oil, various by-products such as palm oil oil, animal and vegetable oil, etc. are used as raw materials, so the physical properties change depending on the composition of the raw material, which results in quality standards. The right mix of raw materials is important. In addition, bio-heavy oil has a very low sulfur and nitrogen content compared to petroleum-based heavy oil (for example, bunker C oil), so it has the effect of reducing harmful emissions such as sulfur oxides (SOx) and nitrogen oxides (NOx). Although it is large, it has a high acid number and low viscosity [Jang Yun-jeong et al., "Study on the quality characteristics of bio heavy oil for power generation as an alternative fuel to heavy oil": Journal of Korean Oil Chem.SOC., Vol.31, No.4, December , 2014, 562-571]. Therefore, bio-heavy oil may inhibit the formation of a lubricant film due to its acidic components, and reduced lubricity can cause friction and wear in fuel supply systems such as fuel pumps, flow pumps, and injectors, resulting in serious damage. there is. In addition, the main components of petroleum-based heavy oil (for example, Bunker C oil) are paraffin, naphthene, and olefin aromatics, but the main components of bio-heavy oil are triglyceride fatty acids, fatty acid methyl esters, As fatty acid ethyl ester, etc., bio-heavy oil has more unsaturated double bonds and contains a large amount of oxygen compared to petroleum-based heavy oil (for example, Bunker C oil), so it has low oxidation stability and high reactivity. As a result, bio-heavy oil can easily be mixed with atmospheric moisture during the storage process, and the moisture content may increase, reducing storage stability. In addition, bio-heavy oil is a product produced by mixing vegetable or animal oils derived from various regions or raw materials, fatty acid esters, and by-products, so sludge is generated depending on the composition of the components. Since it is easy and this can cause problems such as clogging of fuel injection nozzles, it is necessary to secure storage stability by dispersing or dissolving the sludge material in a colloidal state. In addition, bio-heavy oil is generally used by mixing with petroleum-based heavy oil (e.g., Bunker C oil). Bio-heavy oil and petroleum-based heavy oil (e.g., Bunker C oil) There is a problem with poor compatibility because the main ingredients are different.
중유용 연료첨가제와 관련하여 대한민국 등록특허공보 제10-1836946호에는 전체 중량을 기준으로 칼슘 알킬벤젠술포네이트(Calcium alkylbenzenesulfonate) 20~25 중량%; 다이메틸 카보네이트, 다이에틸 카보네이트, 다이프로필 카보네이트, 다이이소프로필 카보네이트, 다이부틸 카보네이트, 다이펜틸 카보네이트, 메틸에틸 카보네이트, 메틸프로필 카보네이트 또는 에틸프로필 카보네이트에서 선택되는 1종 이상의 산소 공급제 30~35 중량%; 히드로처리된 경 증류액(Hydrotreated Light Distillate) 15~20 중량%; 히드로처리된 중 파라핀 증류액(Hydrotreated heavy paraffinic distillate), 히드로처리된 경 파라핀 증류액(Hydrotreated light paraffinic distillate), 용제디왁스된 중 파라핀 증류액(Solvent-dewaxed heavy paraffinic distillate), 용제디왁스된 경 파라핀 증류액(Solvent-dewaxed light paraffinic distillate), 히드로처리 및 디왁스된 중 파라핀 증류액(Hydrotreated and dewaxed heavy paraffinic distillate) 또는 히드로처리 및 디왁스된 경 파라핀 증류액(Hydrotreated and dewaxed light paraffinic distillate)에서 선택되는 1종 이상의 윤활제 3~7 중량%; 소르비탄과 지방산의 에스테르, 폴리에틸렌글리콜과 지방산의 에스테르 또는 폴리에틸렌글리콜 소르비탄과 지방산의 에스테르에서 선택되는 1종 이상의 비이온성 계면활성제 8~15 중량%; 및 C14-C24 분지형 또는 선형 알킬기가 결합된 벤젠술폰산의 과염기성 칼슘염 7~15 중량%을 포함하는 조성물 형태의 중질유용 연료첨가제가 개시되어 있다. 그러나, 상기 선행특허에 개시된 연료첨가제는 석유계 중유에 첨가되어 연소 효율을 향상시키지만, 석유계 중유와 주요 성분 및 물성에서 큰 차이를 보이는 바이오중유(Bio-heavy oil)에 적용하는데에는 한계가 있다.Regarding fuel additives for heavy oil, Republic of Korea Patent Publication No. 10-1836946 contains 20 to 25% by weight of calcium alkylbenzenesulfonate based on the total weight; 30 to 35% by weight of one or more oxygen supply agents selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, or ethyl propyl carbonate. ; Hydrotreated Light Distillate 15-20% by weight; Hydrotreated heavy paraffinic distillate, Hydrotreated light paraffinic distillate, Solvent-dewaxed heavy paraffinic distillate, Solvent-dewaxed light In solvent-dewaxed light paraffinic distillate, hydrotreated and dewaxed heavy paraffinic distillate, or hydrotreated and dewaxed light paraffinic distillate. 3-7% by weight of one or more selected lubricants; 8 to 15% by weight of at least one nonionic surfactant selected from esters of sorbitan and fatty acids, esters of polyethylene glycol and fatty acids, or esters of polyethylene glycol sorbitan and fatty acids; A fuel additive for heavy oil in the form of a composition comprising 7 to 15% by weight of an overbased calcium salt of benzenesulfonic acid to which a C14-C24 branched or linear alkyl group is bonded is disclosed. However, the fuel additive disclosed in the prior patent is added to petroleum-based heavy oil to improve combustion efficiency, but there are limitations in its application to bio-heavy oil, which shows significant differences in major components and physical properties from petroleum-based heavy oil. .
본 발명은 종래의 기술적 배경하에서 도출된 것으로서, 본 발명의 목적은 바이오중유(Bio-heavy oil)에 첨가되어 바이오중유의 윤활성 및 저장 안정성을 개선시키거나, 바이오중유(Bio-heavy oil)와 석유계 중유의 혼화성(Compatibility)을 향상시킬 수 있는 연료첨가제 조성물을 제공하는데에 있다. 또한, 본 발명의 목적은 바이오중유용 연료첨가제 조성물의 용도를 제공하는데에 있다.The present invention was derived from the conventional technical background, and the purpose of the present invention is to improve the lubricity and storage stability of bio-heavy oil by adding it to bio-heavy oil, or to improve the lubricity and storage stability of bio-heavy oil and petroleum oil. The aim is to provide a fuel additive composition that can improve the compatibility of heavy oil. Additionally, the purpose of the present invention is to provide a use of a fuel additive composition for bio heavy oil.
본 발명의 발명자는 다양한 성분들의 조합으로 이루어진 연료첨가제 조성물을 제조하고, 제조한 연료첨가제 조성물을 바이오중유(Bio-heavy oil) 또는 바이오중유(Bio-heavy oil)와 석유계 중유의 혼합유에 첨가한 후, 바이오중유(Bio-heavy oil)의 윤활성 및 저장 안정성 등을 측정한 결과, 연료첨가제 조성물이 특정 성분들의 조합으로 이루어졌을 때 바이오중유(Bio-heavy oil)의 윤활성 및 저장 안정성이 크게 개선되고 바이오중유(Bio-heavy oil)와 석유계 중유의 혼화성(Compatibility)이 크게 향상된다는 점을 확인하고, 본 발명을 완성하였다.The inventor of the present invention manufactured a fuel additive composition consisting of a combination of various ingredients, and added the prepared fuel additive composition to bio-heavy oil or a mixed oil of bio-heavy oil and petroleum-based heavy oil. Afterwards, as a result of measuring the lubricity and storage stability of bio-heavy oil, the lubricity and storage stability of bio-heavy oil were significantly improved when the fuel additive composition consisted of a combination of specific ingredients. It was confirmed that the compatibility between bio-heavy oil and petroleum-based heavy oil was greatly improved, and the present invention was completed.
상기 과제를 해결하기 위하여, 본 발명의 일 예는 전체 중량을 기준으로 벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 20~35 중량%, 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 15~35 중량%, 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 5~25 중량%, 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9) 5~20 중량% 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 10~30 중량%를 포함하는 바이오중유용 연료첨가제 조성물을 제공한다. 또한, 본 발명의 일 예에 따른 바이오중유용 연료첨가제 조성물은 바이오중유(Bio-heavy oil)의 윤활성 및 저장 안정성 개선 효과 등을 고려할 때 바람직하게는 전체 중량을 기준으로 벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 25~30 중량%, 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 20~30 중량%, 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 10~20 중량%, 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9) 10~15 중량% 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 15~25 중량%를 포함한다. 상기 벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 및 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8)은 주로 바이오중유의 슬러지 형성 억제, 분산성 및 저장 안정성 향상에 관여하는 구성성분들이다. 또한, 상기 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 및 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9)은 주로 바이오중유의 윤활성 향상에 관여하는 구성성분들이다. 또한, 상기 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3)은 주로 바이오중유의 연소 촉진에 관여하는 성분들이다. 본 발명의 일 예에 따른 바이오중유용 연료첨가제 조성물은 구성성분들이 본연의 주요 기능을 발휘하면서 동시에 상호 작용으로 시너지 효과 를 발휘하여 바이오중유(Bio-heavy oil)의 윤활성 및 저장 안정성이 크게 개선시키고 바이오중유(Bio-heavy oil)와 석유계 중유의 혼화성(Compatibility)을 크게 향상시킬 수 있다.In order to solve the above problem, an example of the present invention is a mono-C 10-14 -alkyl derivative of benzene (Benzene, mono-C 10-14 -alkyl derivatives; CAS registration number 68442-69-3) based on the total weight. ) 20-35% by weight, Hydrotreated light distillates (CAS registration number 64742-47-8) 15-35% by weight, Pentaerythritol tetraoleate (CAS registration number 19321-40) -5) 5 to 25% by weight, branched, cyclic and linear hydrocarbons with 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 5 ~20% by weight and C 14-24 -branched and linear alkyl derivatives, calcium salts, overbased of Benzenesulfonic acid (CAS registration number 115733-10 ) -3) Provides a fuel additive composition for bio heavy oil containing 10 to 30% by weight. In addition, considering the effect of improving the lubricity and storage stability of bio-heavy oil, the fuel additive composition for bio-heavy oil according to an example of the present invention preferably contains mono-C 10- of benzene based on the total weight. 14 -alkyl derivatives (Benzene, mono-C 10-14 -alkyl derivatives; CAS registration number 68442-69-3) 25~30% by weight, Hydrotreated light distillates (CAS registration number 64742-47- 8) 20-30% by weight, pentaerythritol tetraoleate (CAS registration number 19321-40-5) 10-20% by weight, branched, cyclic and straight-chain hydrocarbon distillate with 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 10-15% by weight and C 14-24 -branched and straight-chain alkyl derivatives of benzenesulfonic acid overbased calcium salts ( Benzenesulfonic acid, C 14-24 -branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3) contains 15 to 25% by weight. Benzene, mono-C 10-14 -alkyl derivatives (CAS registration number 68442-69-3 ) and hydrotreated light distillates (CAS registration number 64742) -47-8) are mainly components involved in suppressing sludge formation and improving dispersibility and storage stability of bio heavy oil. In addition, pentaerythritol tetraoleate (CAS registration number 19321-40-5) and branched, cyclic and straight-chain hydrocarbon distillates having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and Linear hydrocarbons - Distillates; CAS registration number 848301-69-9) are components mainly involved in improving the lubricity of bio heavy oil. In addition, Benzenesulfonic acid, C 14-24 -branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3 ) are mainly ingredients involved in promoting combustion of bio heavy oil. The fuel additive composition for bio-heavy oil according to an example of the present invention greatly improves the lubricity and storage stability of bio-heavy oil by having the components exert their main functions and at the same time exert a synergistic effect through interaction. The compatibility of bio-heavy oil and petroleum-based heavy oil can be greatly improved.
상기 과제를 해결하기 위하여, 본 발명의 일 예는 바이오중유 및 전술한 바이오중유용 연료첨가제 조성물을 포함하는 연료유를 제공한다. 본 발명의 일 예에 따른 연료유는 내에서 연료첨가제 조성물의 함량은 크게 제한되지 않으며, 바이오중유(Bio-heavy oil)의 윤활성 및 저장 안정성 개선 효과 등을 고려할 때 바이오중유 100 중량부 당 0.01 내지 0.2 중량부인 것이 바람직하고, 바이오중유 100 중량부 당 0.015 내지 0.1 중량부인 것이 더 바람직하다.In order to solve the above problem, an example of the present invention provides fuel oil containing bio heavy oil and the above-described fuel additive composition for bio heavy oil. The content of the fuel additive composition in the fuel oil according to an example of the present invention is not greatly limited, and considering the effect of improving the lubricity and storage stability of bio-heavy oil, it is 0.01 to 0.01 parts by weight per 100 parts by weight of bio-heavy oil. It is preferably 0.2 parts by weight, and more preferably 0.015 to 0.1 parts by weight per 100 parts by weight of bio heavy oil.
또한, 본 발명의 다른 예는 석유계 중유, 바이오중유 및 전술한 바이오중유용 연료첨가제 조성물을 포함하는 연료유를 제공한다. 상기 석유계 중유는 원유에서 휘발유·등유·경유 등을 뽑아낸 후 얻어지는 흑갈색의 점성유로서, 이중 연료로 사용되는 석유계 중유는 벙커유(Bunker oil)로 불리운다. 상기 석유계 중유는 벙커A유(Bunker A oil), 벙커B유(Bunker B oil), 벙커C유(Bunker C oil) 등 선박용, 보일러용, 발전용 연료로 사용되는 것이라면 그 종류가 크게 제한되지 않는다. 본 발명의 다른 예에 따른 연료유 내에서 석유계 중유 대 바이오중유의 혼합 중량비는 크게 제한되지 않으며, 예를 들어 2:8 내지 8:2일 수 있고, 3:7 내지 7:3일 수 있다. 또한, 본 발명의 다른 예에 따른 연료유 내에서 연료첨가제 조성물의 함량은 크게 제한되지 않으며 석유계 중유와 바이오중유의 혼화성 향상 효과를 고려할 때 석유계 중유 및 바이오중유의 총합 100 중량부 당 0.01 내지 0.2 중량부인 것이 바람직하고, 석유계 중유 및 바이오중유의 총합 100 중량부 당 0.015 내지 0.1 중량부인 것이 더 바람직하다.In addition, another example of the present invention provides fuel oil containing petroleum-based heavy oil, bio heavy oil, and the above-described fuel additive composition for bio heavy oil. The petroleum-based heavy oil is a dark brown viscous oil obtained after extracting gasoline, kerosene, diesel, etc. from crude oil. Petroleum-based heavy oil used as a fuel is called bunker oil. The types of petroleum heavy oil are not greatly limited as long as they are used as fuel for ships, boilers, and power generation, such as Bunker A oil, Bunker B oil, and Bunker C oil. No. The mixing weight ratio of petroleum heavy oil to bio heavy oil in the fuel oil according to another example of the present invention is not greatly limited, and may be, for example, 2:8 to 8:2, and 3:7 to 7:3. . In addition, the content of the fuel additive composition in the fuel oil according to another example of the present invention is not greatly limited, and considering the effect of improving the miscibility of petroleum heavy oil and bio heavy oil, the total amount of petroleum heavy oil and bio heavy oil is 0.01 per 100 parts by weight. It is preferably from 0.2 parts by weight, and more preferably from 0.015 to 0.1 parts by weight per 100 parts by weight of the total of petroleum heavy oil and bio heavy oil.
본 발명에 따른 바이오중유용 연료첨가제 조성물은 바이오중유(Bio-heavy oil)의 윤활성 및 저장 안정성이 크게 개선시키거나, 바이오중유(Bio-heavy oil)와 석유계 중유의 혼화성(Compatibility)을 크게 향상시킬 수 있다. 따라서, 본 발명예 따른 바이오중유용 연료첨가제 조성물을 사용하면 바이오중유(Bio-heavy oil)로부터 발생되는 문제점들을 해결할 수 있고, 바이오중유(Bio-heavy oil)의 적용 범위를 크게 넓힐 수 있다.The fuel additive composition for bio-heavy oil according to the present invention significantly improves the lubricity and storage stability of bio-heavy oil, or greatly improves the compatibility between bio-heavy oil and petroleum-based heavy oil. It can be improved. Therefore, by using the fuel additive composition for bio-heavy oil according to the present invention, problems arising from bio-heavy oil can be solved and the scope of application of bio-heavy oil can be greatly expanded.
이하, 본 발명을 실시예를 통하여 구체적으로 설명한다. 다만, 하기 실시예는 본 발명의 기술적 특징을 명확하게 예시하기 위한 것일 뿐, 본 발명의 보호 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in detail through examples. However, the following examples are only intended to clearly illustrate the technical features of the present invention and do not limit the scope of protection of the present invention.
1. 연료첨가제 조성물의 제조1. Preparation of fuel additive composition
제조예 1.Manufacturing Example 1.
벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 28 중량부, 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 23 중량부, 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 20 중량부, 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9) 14 중량부 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 15 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.Benzene, mono- C10-14 -alkyl derivatives (CAS registration number 68442-69-3) 28 parts by weight, Hydrotreated light distillates (CAS registration number) 64742-47-8) 23 parts by weight, pentaerythritol tetraoleate (CAS registration number 19321-40-5) 20 parts by weight, branched, cyclic and straight-chain hydrocarbon distillate having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 14 parts by weight and C 14-24 -branched and straight chain alkyl derivatives of benzenesulfonic acid , C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3) were mixed uniformly to prepare a fuel additive composition.
제조예 2.Manufacturing example 2.
벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 30 중량부, 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 20 중량부, 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 10 중량부, 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9) 15 중량부 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 25 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.30 parts by weight of Benzene, mono- C10-14 -alkyl derivatives (CAS registration number 68442-69-3), Hydrotreated light distillates (CAS registration number) 64742-47-8) 20 parts by weight, pentaerythritol tetraoleate (CAS registration number 19321-40-5) 10 parts by weight, distillate of branched, cyclic and straight-chain hydrocarbons having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 15 parts by weight and C 14-24 -branched and linear alkyl derivatives of benzenesulfonic acid , C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3) were mixed uniformly to prepare a fuel additive composition.
제조예 3.Manufacturing example 3.
벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 25 중량부, 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 30 중량부, 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 15 중량부, 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9) 10 중량부 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 20 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.25 parts by weight of Benzene, mono- C10-14 -alkyl derivatives (CAS registration number 68442-69-3), Hydrotreated light distillates (CAS registration number) 64742-47-8) 30 parts by weight, pentaerythritol tetraoleate (CAS registration number 19321-40-5) 15 parts by weight, branched, cyclic and straight-chain hydrocarbon distillate having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 10 parts by weight and C 14-24 -branched and linear alkyl derivatives of benzenesulfonic acid , C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3) were mixed uniformly to prepare a fuel additive composition.
비교제조예 1.Comparative manufacturing example 1.
히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 51 중량부, 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9) 34 중량부 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 15 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.Hydrotreated light distillates (CAS registration number 64742-47-8) 51 parts by weight, branched, cyclic and straight-chain hydrocarbon distillates having 18 to 50 carbon atoms (C 18 -C 50 branched, cyclic and linear hydrocarbons - Distillates; CAS registration number 848301-69-9) 34 parts by weight C 14-24 -branched and linear alkyl derivatives of benzenesulfonic acid , calcium salts, overbased; CAS registration number 115733-10-3) was mixed uniformly to prepare a fuel additive composition.
비교제조예 2.Comparative manufacturing example 2.
히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 51 중량부, 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 34 중량부 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 15 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.Hydrotreated light distillates (CAS registration number 64742-47-8) 51 parts by weight, Pentaerythritol tetraoleate (CAS registration number 19321-40-5) 34 parts by weight and benzenesulfonic acid 15 parts by weight of C 14-24 -branched and linear alkyl derivatives, calcium salts, overbased (CAS registration number 115733-10-3) uniformly A fuel additive composition was prepared by mixing.
비교제조예 3.Comparative manufacturing example 3.
벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 48 중량부, 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 37 중량부 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 15 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.48 parts by weight of Benzene, mono- C10-14 -alkyl derivatives (CAS registration number 68442-69-3), Hydrotreated light distillates (CAS registration number) 64742-47-8) 37 parts by weight and C 14-24 -branched and linear alkyl derivatives of benzenesulfonic acid (Benzenesulfonic acid, C 14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS registered) Number 115733-10-3) A fuel additive composition was prepared by uniformly mixing 15 parts by weight.
2. 바이오중유 기반 연료유 제조 및 물성 측정2. Production of bio heavy oil-based fuel oil and measurement of physical properties
팜산유(Palm acid oil) 40 중량%, 동물성 유지(Animal oil) 15 중량%, 지방산 메틸에스테르(Fatty acid methyl ester) 20 중량%, 바이오디젤 피치(Biodiesel pitch) 25 중량%로 구성된 바이오중유를 준비하였다. 준비한 바이오중유에 제조예 1 내지 제조예 3 및 비교제조예 1 내지 비교제조예 3에서 제조한 연료첨가제 조성물을 각각 200 ppm의 양이 되게 첨가하고 혼합하여 연료유를 제조하였다.Prepare bio heavy oil consisting of 40% by weight of palm acid oil, 15% by weight of animal oil, 20% by weight of fatty acid methyl ester, and 25% by weight of biodiesel pitch. did. The fuel additive compositions prepared in Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 3 were added to the prepared bio heavy oil in an amount of 200 ppm and mixed to prepare fuel oil.
(1) 연료유의 윤활성 측정(1) Measurement of lubricity of fuel oil
ASTM D6079 표준 시험법에 포함되는 HFRR(High-Frequency Reciprocating Rig) 시험법을 사용하여 연료유의 윤활성을 측정하였다. HFRR 시험법은 디젤 연료의 윤활성을 평가하는 방법으로서, 측정 값은 마이크로미터(㎛) 단위로 제공되며, 값이 낮을수록 윤활성이 좋다는 것을 의미한다. 하기 표 1에 바이오중유 기반 연료유의 윤활성 측정 값을 정리하였다.The lubricity of fuel oil was measured using the HFRR (High-Frequency Reciprocating Rig) test method included in the ASTM D6079 standard test method. The HFRR test method is a method of evaluating the lubricity of diesel fuel. Measured values are provided in micrometers (㎛), and the lower the value, the better the lubricity. Table 1 below summarizes the lubricity measurement values of bio heavy oil-based fuel oil.
연료유 시료 구분Fuel oil sample classification 연료유에 첨가된 연료첨가제 조성물 구분Classification of fuel additive compositions added to fuel oil HFRR(㎛)HFRR(㎛)
연료유 1fuel oil 1 제조예 1Manufacturing Example 1 130130
연료유 2fuel oil 2 제조예 2Production example 2 135135
연료유 3fuel oil 3 제조예 3Production example 3 140140
연료유 4fuel oil 4 비교제조예 1Comparative Manufacturing Example 1 290290
연료유 5fuel oil 5 비교제조예 2Comparative Manufacturing Example 2 275275
연료유 6fuel oil 6 비교제조예 3Comparative Manufacturing Example 3 430430
(2) 연료유의 저장 안정성 측정(2) Measurement of storage stability of fuel oil
ASTM D4740 표준 시험법에 포함되는 반점분석법 Spot Test를 사용하여 연료유의 저장 안정성을 측정하였다. 상기 Spot Test는 연료유 내의 슬러지 생성 등과 같은 연료유 자체의 안정성을 측정하거나 서로 다른 연료들의 혼화성을 측정하는데에 사용되며, 측정 값은 스팟 등급(Spot rating) 1, 2, 3, 4 및 5와 같이 5개의 등급으로 제공되며, 스팟 등급(Spot rating) 1에 가까울수록 저장 안정성 또는 혼화성이 양호하고, 스팟 등급(Spot rating) 5에 가까울수록 저장 안정성 또는 혼화성이 떨어진다는 것을 의미한다. 하기 표 2에 스팟 등급(Spot rating)에 따른 판정 기준을 정리하였다.The storage stability of fuel oil was measured using the spot test, which is included in the ASTM D4740 standard test method. The Spot Test is used to measure the stability of fuel oil itself, such as sludge production in fuel oil, or to measure the miscibility of different fuels, and the measured values are spot ratings 1, 2, 3, 4, and 5. It is provided in five grades, and the closer it is to a spot rating of 1, the better the storage stability or miscibility, and the closer it is to a spot rating of 5, the worse the storage stability or miscibility is. Table 2 below summarizes the judgment criteria according to spot rating.
스팟 등급
(Spot rating)spot rating
(Spot rating) 		판정 기준Criteria
1One 균질한 스팟(내부링 없음)/ Homogeneous spot (no inner ring)Homogeneous spot (no inner ring)
22 희미하거나 약하게 표시된 내부링/ Faint or poorly defined inner ringFaint or poorly defined inner ring
33 잘 구분되는 얇은 내부링, 배경색보다 약간 어두운 색을 나타냄/ Well-defined thin inner ring, only slightly darker than the backgroundWell-defined thin inner ring, only slightly darker than the background
44 잘 구분되는 내부링, 스팟 등급 3의 링보다 더 두껍고 배경색보다 좀 더 진한 색상, / Well-defined inner ring, thicker than the ring in reference spot No. 3 and somewhat darker than the background/ Well-defined inner ring, thicker than the ring in reference spot No. 3 and somewhat darker than the background
55 중심에 매우 어두운 고체상 부분이 존재함, 중심 부분의 색상이 배경 부분보다 어두움/ Very dark solid or nearly solid area in the center. The central area is much darker than the backgroundVery dark solid or nearly solid area in the center. The color of the center is darker than the background. The central area is much darker than the background
하기 표 3에 바이오중유 기반 연료유의 저장 안정성 측정 값을 정리하였다.Table 3 below summarizes the storage stability measurements of bioheavy oil-based fuel oil.
연료유 시료 구분Fuel oil sample classification 연료유에 첨가된 연료첨가제 조성물 구분Classification of fuel additive compositions added to fuel oil 스팟 등급spot rating
연료유 1fuel oil 1 제조예 1Manufacturing Example 1 1One
연료유 2fuel oil 2 제조예 2Production example 2 1One
연료유 3fuel oil 3 제조예 3Production example 3 1One
연료유 4fuel oil 4 비교제조예 1Comparative Manufacturing Example 1 33
연료유 5fuel oil 5 비교제조예 2Comparative Manufacturing Example 2 33
연료유 6fuel oil 6 비교제조예 3Comparative Manufacturing Example 3 1One
3. 벙커C유(Bunker C oil)와 바이오중유 기반 혼합 연료유 제조 및 물성 측정3. Manufacturing and measuring physical properties of mixed fuel oil based on Bunker C oil and bio heavy oil
팜산유(Palm acid oil) 40 중량%, 동물성 유지(Animal oil) 15 중량%, 지방산 메틸에스테르(Fatty acid methyl ester) 20 중량%, 바이오디젤 피치(Biodiesel pitch) 25 중량%로 구성된 바이오중유를 준비하였다. 준비한 바이오중유와 벙커C유를 1:1의 중량비로 혼합하여 혼합 중유를 제조하였다. 이후, 혼합 중유에 제조예 1 내지 제조예 3 및 비교제조예 1 내지 비교제조예 3에서 제조한 연료첨가제 조성물을 각각 200 ppm의 양이 되게 첨가하고 혼합하여 혼합 연료유를 제조하였다.Prepare bio heavy oil consisting of 40% by weight of palm acid oil, 15% by weight of animal oil, 20% by weight of fatty acid methyl ester, and 25% by weight of biodiesel pitch. did. Mixed heavy oil was prepared by mixing the prepared bio heavy oil and bunker C oil at a weight ratio of 1:1. Thereafter, the fuel additive compositions prepared in Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 3 were added to the mixed heavy oil in an amount of 200 ppm and mixed to prepare mixed fuel oil.
상기 혼합 연료유의 혼화성(Compatibility)을 ASTM D4740 표준 시험법에 포함되는 반점분석법 Spot Test를 사용하여 측정하였고, 하기 표 4에 벙커C유(Bunker C oil)와 바이오중유 기반 혼합 연료유의 혼화성 측정 값을 정리하였다.The compatibility of the mixed fuel oil was measured using the Spot Test included in the ASTM D4740 standard test method, and the compatibility of Bunker C oil and bio heavy oil-based mixed fuel oil is measured in Table 4 below. The values have been organized.
연료유 시료 구분Fuel oil sample classification 연료유에 첨가된 연료첨가제 조성물 구분Classification of fuel additive compositions added to fuel oil 스팟 등급spot rating
혼합 연료유 1Blended fuel oil 1 제조예 1Manufacturing Example 1 1One
혼합 연료유 2Blended fuel oil 2 제조예 2Production example 2 1One
혼합 연료유 3Blended fuel oil 3 제조예 3Production example 3 1One
혼합 연료유 4Blended fuel oil 4 비교제조예 1Comparative Manufacturing Example 1 33
혼합 연료유 5Blended fuel oil 5 비교제조예 2Comparative Manufacturing Example 2 33
혼합 연료유 6Blended fuel oil 6 비교제조예 3Comparative Manufacturing Example 3 1One
이상에서와 같이 본 발명을 상기의 실시예를 통해 설명하였지만 본 발명의 보호범위가 반드시 여기에만 한정되는 것은 아니며 본 발명의 범주와 사상을 벗어나지 않는 범위 내에서 다양한 변형실시가 가능함은 물론이다. 따라서, 본 발명의 보호범위는 본 발명에 첨부된 특허청구의 범위에 속하는 모든 실시 형태를 포함하는 것으로 해석되어야 한다.As described above, the present invention has been described through the above-mentioned embodiments, but the scope of protection of the present invention is not necessarily limited thereto, and of course, various modifications are possible without departing from the scope and spirit of the present invention. Accordingly, the scope of protection of the present invention should be interpreted to include all embodiments falling within the scope of the patent claims attached to the present invention.

Claims (6)

  1. 전체 중량을 기준으로 벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 20~35 중량%, 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 15~35 중량%, 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 5~25 중량%, 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9) 5~20 중량% 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 10~30 중량%를 포함하는 바이오중유용 연료첨가제 조성물.20-35% by weight of Benzene, mono-C 10-14 -alkyl derivatives (CAS registration number 68442-69-3), hydrotreated light distillate, based on total weight (Hydrotreated light distillates; CAS registration number 64742-47-8) 15 to 35% by weight, pentaerythritol tetraoleate (CAS registration number 19321-40-5) 5 to 25% by weight, carbon number 18 to 50 Branched, cyclic and linear hydrocarbons - Distillates (CAS registration number 848301-69-9) with 5-20% by weight and C 14-24 of benzenesulfonic acid - In biomass containing 10-30% by weight of branched and straight - chain alkyl derivatives, calcium salts, overbased (CAS registration number 115733-10-3). Useful fuel additive composition.
  2. 제1항에 있어서, 전체 중량을 기준으로 벤젠의 모노-C10-14-알킬 유도체(Benzene, mono-C10-14-alkyl derivatives; CAS 등록번호 68442-69-3) 25~30 중량%, 히드로처리된 경 증류액(Hydrotreated light distillates; CAS 등록번호 64742-47-8) 20~30 중량%, 펜타에리쓰리톨 테트라올레이트(Pentaerythritol tetraoleate; CAS 등록번호 19321-40-5) 10~20 중량%, 탄소수 18 내지 50을 가진 분지형, 환형 및 직쇄형 탄화수소 증류액(C18-C50 branched, cyclic and linear hydrocarbons - Distillates; CAS 등록번호 848301-69-9) 10~15 중량% 및 벤젠술폰산의 C14-24-분지형 및 직쇄형 알킬 유도체 과염기성 칼슘염(Benzenesulfonic acid, C14-24-branched and linear alkyl derivatives, calcium salts, overbased; CAS 등록번호 115733-10-3) 15~25 중량%를 포함하는 바이오중유용 연료첨가제 조성물.25 to 30% by weight of benzene, mono-C 10-14 -alkyl derivatives (CAS registration number 68442-69-3 ), based on the total weight, Hydrotreated light distillates (CAS registration number 64742-47-8) 20-30% by weight, Pentaerythritol tetraoleate (CAS registration number 19321-40-5) 10-20% by weight %, 10-15% by weight of branched, cyclic and linear hydrocarbons - Distillates with 18 to 50 carbon atoms (CAS registration number 848301-69-9) and benzenesulfonic acid. Benzenesulfonic acid, C 14-24 -branched and linear alkyl derivatives, calcium salts, overbased; CAS registration number 115733-10-3 ) 15~25 Weight A fuel additive composition for bio heavy oil containing %.
  3. 바이오중유; 및 제1항 또는 제2항의 바이오중유용 연료첨가제 조성물을 포함하는 연료유.bio heavy oil; And fuel oil containing the fuel additive composition for bio heavy oil of claim 1 or 2.
  4. 제3항에 있어서, 상기 연료유 내에서 연료첨가제 조성물의 함량은 바이오중유 100 중량부 당 0.01 내지 0.2 중량부인 것을 특징으로 하는 연료유.The fuel oil according to claim 3, wherein the content of the fuel additive composition in the fuel oil is 0.01 to 0.2 parts by weight per 100 parts by weight of bio heavy oil.
  5. 석유계 중유; 바이오중유; 및 제1항 또는 제2항의 바이오중유용 연료첨가제 조성물을 포함하는 연료유.Petroleum-based heavy oil; bio heavy oil; And fuel oil containing the fuel additive composition for bio heavy oil of claim 1 or 2.
  6. 제5항에 있어서, 상기 연료유 내에서 석유계 중유 대 바이오중유의 혼합 중량비는 2:8 내지 8:2이고, 연료첨가제 조성물의 함량은 석유계 중유 및 바이오중유의 총합 100 중량부 당 0.01 내지 0.2 중량부인 것을 특징으로 하는 연료유.The method of claim 5, wherein the mixing weight ratio of petroleum heavy oil to bio heavy oil in the fuel oil is 2:8 to 8:2, and the content of the fuel additive composition is 0.01 to 100 parts by weight of the total of petroleum heavy oil and bio heavy oil. Fuel oil characterized in that it is 0.2 parts by weight.
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