본 발명은 연료첨가제 조성물 등에 관한 것으로서, 더 상세하게는 휘발유, 경유, 중유 등과 같은 다양한 연료에 첨가되어 연료 연소시 연소 효율을 향상시키고 동시에 미세입자(particulate matter, PM), 일산화탄소(CO), 탄화수소(HC), 질소산화물(NOx) 등과 같은 대기 오염물질의 발생을 크게 감소시킬 수 있는 범용 연료첨가제 조성물 및 이의 용도에 관한 것이다.The present invention relates to a fuel additive composition and the like, and more specifically, to a general-purpose fuel additive composition which can be added to various fuels such as gasoline, diesel, and heavy oil to improve combustion efficiency during fuel combustion and at the same time significantly reduce the generation of air pollutants such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NOx), and its use.
일반적으로 산업체에서는 주로 화석연료를 사용하고 있는데, 화석연료 연소시 질소산화물(NOx), 황산화물(SOx), 일산화탄소(CO), 분진 등과 같은 물질이 배출되어 환경을 오염시키고 지구 온난화를 가속시키고 있다. 특히, 미세입자(particulate matter, PM), 오존, 질소산화물(NOx), 황산화물(SOx), 휘발성 유기화합물(VOC) 등은 시정장애를 일으키고 인체 및 재산상의 직간접 피해를 크게 유발하는 원인물질로 중요하게 대두되고 있다.In general, industries mainly use fossil fuels, and when fossil fuels are burned, substances such as nitrogen oxides (NOx), sulfur oxides (SOx), carbon monoxide (CO), and dust are emitted, polluting the environment and accelerating global warming. In particular, particulate matter (PM), ozone, nitrogen oxides (NOx), sulfur oxides (SOx), and volatile organic compounds (VOCs) are emerging as important causative substances that cause visibility impairment and direct and indirect damage to human bodies and property.
세계 각국은 지구 온난화 방지 및 지구 환경을 파괴하는 대기 오염물질을 저감 하기 위해 배출 허용기준을 점차 강화하고 있다. 따라서, 화석연료를 사용하는 보일러나 다양한 내연기관에서 연료 연소시 각종 대기 오염을 감소시키고 에너지 소비 효율을 높이기 위한 기술이 요구된다. 운항 중인 선박에는 입자상 유해물질을 감소시키기 위해 집진시설을 설치할 필요가 있으나, 환경적 또는 경제적 측면에서 가장 바람직한 것은 연소로 내에서 연소 효율을 높여 완전 연소가 이루어지게 하고 연소로내 자체에서 미세먼지의 생성을 크게 줄일 수 있는 청정기술의 개발이 우선적으로 중요하다.Countries around the world are gradually strengthening emission standards to prevent global warming and reduce air pollutants that destroy the global environment. Therefore, technologies are required to reduce various air pollution and increase energy consumption efficiency when burning fuel in boilers or various internal combustion engines using fossil fuels. It is necessary to install dust collection facilities on ships in operation to reduce particulate matter, but the most desirable thing from an environmental or economic perspective is to increase combustion efficiency in the combustion furnace to ensure complete combustion and to develop clean technologies that can significantly reduce the generation of fine dust within the combustion furnace itself.
최근들어 화석연료의 연소로부터 보다 큰 연소 효율을 얻으면서도 오염물의 생성 및 배출을 억제할 필요성에 대해 경각심이 증가하고 있으며, 이러한 목적을 달성하기 위해 연료에 첨가하는 연료첨가제가 다양하게 개발 및 사용되었다. 예를 들어, 대한민국 등록특허공보 제10-1836946호에는 전체 중량을 기준으로 유용성 금속화합물(Oil soluble metallic compound) 20~25 중량%, 산소 공급제 30~35 중량%, 분산제 15~20 중량%, 윤활제 3~7 중량%, 비이온성 계면활성제 8~15 중량% 및 과염기성 청정제(Overbased detergent) 7~15 중량%을 포함하는 중질유용 연료첨가제가 개시되어 있다. 또한, 대한민국 등록특허공보 제10-2503500호에는 수소 처리된 중질 파라핀 정제유[Distillates (petroleum), hydrotreated heavy paraffinic] 97 wt%, 수소 처리된 중질 나프타[Naphtha (petroleum), Hydrotreated heavy] 0.3 wt%, 나프탈렌(Naphthalene) 0.3 wt%, 수소탈황화된 케로젠(Hydrosulfurized Kerosene) 0.3 wt%, 지방산 메틸 에스터(Fatty acid methyl ester) 0.3 wt%, 폴리올 에스테르(Polyol Esters) 0.3 wt%, 폴리올레핀 알킬페놀 알킬아민(Polyolefin alkylphenol alkylamine) 0.3 wt%, 나프타(석유) 중질 방향족 화합물(Solvent naphtha, petroleum, heavy aromatic) 0.3 wt%, 팔미트산(Palmitic acid) 0.3 wt%, 2-(2-부톡시에톡시)에탄올(2-(2-butoxyethoxy)ethanol) 및 2-에틸-1-헥산올(2-ethyl-1-hexanol) 0.3 wt%를 포함하는, 연료첨가제 조성물이 개시되어 있다.Recently, there has been a growing awareness of the need to obtain greater combustion efficiency from the combustion of fossil fuels while suppressing the creation and emission of pollutants, and various fuel additives added to fuel have been developed and used to achieve this purpose. For example, Korean Patent Publication No. 10-1836946 discloses a heavy oil fuel additive comprising 20 to 25 wt% of an oil soluble metallic compound, 30 to 35 wt% of an oxygen supply agent, 15 to 20 wt% of a dispersant, 3 to 7 wt% of a lubricant, 8 to 15 wt% of a nonionic surfactant, and 7 to 15 wt% of an overbased detergent, based on the total weight. In addition, Korean Patent Publication No. 10-2503500 discloses a composition comprising 97 wt% of Distillates (petroleum), hydrotreated heavy paraffinic, 0.3 wt% of Naphtha (petroleum), Hydrotreated heavy, 0.3 wt% of Naphthalene, 0.3 wt% of Hydrosulfurized Kerosene, 0.3 wt% of Fatty acid methyl ester, 0.3 wt% of Polyol Esters, 0.3 wt% of Polyolefin alkylphenol alkylamine, 0.3 wt% of Solvent naphtha, petroleum, heavy aromatic, A fuel additive composition comprising 0.3 wt% of palmitic acid, 0.3 wt% of 2-(2-butoxyethoxy)ethanol and 2-ethyl-1-hexanol is disclosed.
본 발명은 종래의 기술적 배경하에서 도출된 것으로서, 본 발명의 목적은 휘발유, 경유, 중유 등과 같은 다양한 연료에 첨가되어 연료 연소시 연소 효율을 향상시키고 동시에 미세입자(particulate matter, PM), 일산화탄소(CO), 탄화수소(HC), 질소산화물(NOx) 등과 같은 대기 오염물질의 발생을 크게 감소시킬 수 있는 연료첨가제 조성물을 제공하는데에 있다. 또한, 본 발명의 목적은 연료첨가제 조성물의 용도를 제공하는데에 있다.The present invention has been derived under the conventional technical background, and an object of the present invention is to provide a fuel additive composition which can be added to various fuels such as gasoline, diesel, heavy oil, etc. to improve combustion efficiency during fuel combustion and at the same time significantly reduce the generation of air pollutants such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NOx), etc. In addition, an object of the present invention is to provide a use of the fuel additive composition.
본 발명의 발명자들은 산화방지제, 부식방지제, 연소촉진제, 청정제 및 분산제 각각에 해당하는 다양한 성분들을 스크리닝하고 조합하여 연료첨가제 조성물을 제조하였다. 이후, 본 발명의 발명자들은 제조한 연료첨가제 조성물을 휘발유, 경유, 중유 등과 같은 다양한 연료에 첨가하고 연소 특성을 분석한 결과, 특정 성분들의 조합으로 이루어진 연료첨가제 조성물이 연료의 종류와 상관없이 범용적으로 연소 효율을 향상시키고 동시에 미세입자(particulate matter, PM), 일산화탄소(CO), 탄화수소(HC), 질소산화물(NOx) 등과 같은 대기 오염물질의 발생을 크게 감소시킬 수 있다는 점을 확인하였다.The inventors of the present invention screened and combined various components corresponding to antioxidants, corrosion inhibitors, combustion promoters, detergents, and dispersants, respectively, to prepare a fuel additive composition. Thereafter, the inventors of the present invention added the prepared fuel additive composition to various fuels such as gasoline, diesel, and heavy oil, and analyzed the combustion characteristics. As a result, it was confirmed that a fuel additive composition composed of a combination of specific components can universally improve combustion efficiency regardless of the type of fuel, and at the same time significantly reduce the generation of air pollutants such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NOx).
상기 과제를 해결하기 위하여, 본 발명의 일 예는 tert-부틸하이드로퀴논(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0), 칼슘석유술폰산염(Calcium petroleum sulfonate; CAS 등록번호 : 61789-86-4), 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1), 과염기성 칼슘석유술폰산염(Overbased calcium petroleum sulfonate; CAS 등록번호 : 68783-96-0), 솔비탄모노라우레이트(Sorbitan monolaurate; CAS 등록번호 : 1338-39-2) 및 2-에틸헥실 질산염(2-Ethylhexyl nitrate; CAS 등록번호 : 27247-96-7)으로 이루어지거나 이들을 포함하는 연료첨가제 조성물을 제공한다. 본 발명의 일 예에 따른 연료첨가제 조성물은 연료의 연소 효율 향상 및 대기 오염물질의 발생 억제 등을 고려할 때 전체 중량을 기준으로 tert-부틸하이드로퀴논(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0) 10~20 중량%, 칼슘석유술폰산염(Calcium petroleum sulfonate; CAS 등록번호 : 61789-86-4) 5~15 중량%, 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1) 20~35 중량%, 과염기성 칼슘석유술폰산염(Overbased calcium petroleum sulfonate; CAS 등록번호 : 68783-96-0) 10~20 중량%, 솔비탄모노라우레이트(Sorbitan monolaurate; CAS 등록번호 : 1338-39-2) 24~40 중량% 및 2-에틸헥실 질산염(2-Ethylhexyl nitrate; CAS 등록번호 : 27247-96-7) 4~12 중량%를 포함하는 것이 바람직하고, 전체 중량을 기준으로 tert-부틸하이드로퀴논(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0) 12~18 중량%, 칼슘석유술폰산염(Calcium petroleum sulfonate; CAS 등록번호 : 61789-86-4) 8~14 중량%, 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1) 22~30 중량%, 과염기성 칼슘석유술폰산염(Overbased calcium petroleum sulfonate; CAS 등록번호 : 68783-96-0) 12~18 중량%, 솔비탄모노라우레이트(Sorbitan monolaurate; CAS 등록번호 : 1338-39-2) 25~35 중량% 및 2-에틸헥실 질산염(2-Ethylhexyl nitrate; CAS 등록번호 : 27247-96-7) 5~10 중량%를 포함하는 것이 더 바람직하다. 본 발명의 일 예에 따른 연료첨가제 조성물은 구성성분들이 본연의 주요 기능을 발휘하면서 동시에 상호 작용으로 시너지 효과를 발휘하여 연소 효율을 향상시키고 동시에 미세입자(particulate matter, PM), 일산화탄소(CO), 탄화수소(HC), 질소산화물(NOx) 등과 같은 대기 오염물질의 발생을 크게 감소시킬 수 있다. 또한, 본 발명의 일 예에 따른 연료첨가제 조성물은 바이오중유(Bio-heavy oil) 또는 석유계 중유와 바이오중유(Bio-heavy oil)의 혼합 중유의 산화를 억제하고 저장 안정성을 크게 개선시킬 수 있다.In order to solve the above problem, one example of the present invention provides a fuel additive composition comprising or including tert-butylhydroquinone (CAS Registry Number: 1948-33-0), calcium petroleum sulfonate (CAS Registry Number: 61789-86-4), calcium acetylacetonate hydrate (CAS Registry Number: 345909-31-1), overbased calcium petroleum sulfonate (CAS Registry Number: 68783-96-0), sorbitan monolaurate (CAS Registry Number: 1338-39-2), and 2-ethylhexyl nitrate (CAS Registry Number: 27247-96-7). Provided. According to an example of the present invention, a fuel additive composition, when considering the improvement of combustion efficiency of fuel and the suppression of the generation of air pollutants, contains 10 to 20 wt% of tert-butylhydroquinone (CAS registration number: 1948-33-0), 5 to 15 wt% of calcium petroleum sulfonate (CAS registration number: 61789-86-4), 20 to 35 wt% of calcium acetylacetonate hydrate (CAS registration number: 345909-31-1), 10 to 20 wt% of overbased calcium petroleum sulfonate (CAS registration number: 68783-96-0), and sorbitan monolaurate (CAS registration number: 68783-96-0), based on the total weight. It is preferable that the composition comprises 24 to 40 wt% of tert-butylhydroquinone (CAS Registry Number: 1948-33-0), 8 to 14 wt% of calcium petroleum sulfonate (CAS Registry Number: 61789-86-4), 22 to 30 wt% of calcium acetylacetonate hydrate (CAS Registry Number: 345909-31-1), and 4 to 12 wt% of 2-ethylhexyl nitrate (CAS Registry Number: 27247-96-7), based on the total weight. It is more preferable that the fuel additive composition comprises 12 to 18 wt% of sorbitan monolaurate (CAS registry number: 1338-39-2), 25 to 35 wt% of sorbitan monolaurate (CAS registry number: 1338-39-2), and 5 to 10 wt% of 2-ethylhexyl nitrate (CAS registry number: 27247-96-7). The fuel additive composition according to an example of the present invention can improve combustion efficiency and significantly reduce the generation of air pollutants such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NOx) by allowing the components to exhibit their original main functions while simultaneously exhibiting a synergistic effect through interaction. In addition, a fuel additive composition according to an example of the present invention can inhibit oxidation of bio-heavy oil or a mixed heavy oil of petroleum-based heavy oil and bio-heavy oil and significantly improve storage stability.
상기 과제를 해결하기 위하여, 본 발명의 일 예는 휘발유, 경유 및 중유로 이루어진 군에서 선택되는 어느 하나의 액체 연료; 전술한 연료첨가제 조성물을 포함하는 연료유(Fuel oil)를 제공한다. 본 발명의 연료유 내에서 연료첨가제 조성물의 함량은 크게 제한되지 않으며, 연료의 연소 효율 향상 및 대기 오염물질의 발생 억제 등을 고려할 때 액체 연료 100ℓ 대비 0.01ℓ 내지 0.5ℓ인 것이 바람직하고, 액체 연료 100ℓ 대비 0.02ℓ 내지 0.25ℓ인 것이 더 바람직하다. 상기 중유는 석유계 중유, 바이오중유(Bio-heavy oil) 또는 석유계 중유와 바이오중유의 혼합 중유에서 선택될 수 있다. 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. 또한, 상기 바이오중유는 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. 상기 혼합 중유 내에서 석유계 중유 대 바이오중유의 혼합 중량비는 크게 제한되지 않으며, 8:2 내지 2:8일 수 있고, 7:3 내지 3:7일 수 있다.In order to solve the above problem, one example of the present invention provides a fuel oil comprising any one liquid fuel selected from the group consisting of gasoline, kerosene, and heavy oil; and the fuel additive composition described above. The content of the fuel additive composition in the fuel oil of the present invention is not particularly limited, and in consideration of improving combustion efficiency of the fuel and suppressing the generation of air pollutants, it is preferably 0.01 to 0.5 ℓ per 100 ℓ of liquid fuel, and more preferably 0.02 to 0.25 ℓ per 100 ℓ of liquid fuel. The heavy oil may be selected from petroleum-based heavy oil, bio-heavy oil, or a mixed heavy oil of petroleum-based heavy oil and bio-heavy oil. The petroleum-based heavy oil is a dark brown viscous oil obtained after extracting gasoline, kerosene, kerosene, etc. from crude oil, and among these, the petroleum-based heavy oil used as fuel is called bunker oil. The above petroleum heavy oil is not particularly limited in type as long as it is used as fuel for ships, boilers, and power generation, such as Bunker A oil, Bunker B oil, and Bunker C oil. In addition, the bio-heavy oil is a biofuel manufactured by reacting unused resources such as biodiesel process by-products (pitch), waste animal fat, waste vegetable fat, and palm by-products with methanol or ethanol, and has similar properties to petroleum heavy oil (e.g., Bunker C oil), so it can be used by mixing with petroleum heavy oil, or has recently attracted attention as an eco-friendly fuel that can 100% replace petroleum heavy oil. The mixing weight ratio of petroleum heavy oil to bio-heavy oil in the above mixed heavy oil is not particularly limited, and can be 8:2 to 2:8, or 7:3 to 3:7.
본 발명의 일 예에 따른 연료첨가제 조성물은 휘발유, 경유, 중유 등과 같은 다양한 연료에 첨가되어 연료 연소시 연소 효율을 향상시키고 동시에 미세입자(particulate matter, PM), 일산화탄소(CO), 탄화수소(HC), 질소산화물(NOx) 등과 같은 대기 오염물질의 발생을 크게 감소시킬 수 있다. 또한, 본 발명의 일 예에 따른 연료첨가제 조성물은 바이오중유(Bio-heavy oil) 또는 석유계 중유와 바이오중유(Bio-heavy oil)의 혼합 중유의 산화를 억제하고 저장 안정성을 크게 개선시킬 수 있다. 따라서, 본 발명의 일 예에 따른 연료첨가제 조성물은 지구 온난화 및 대기오염 방지에 기여할 수 있다.A fuel additive composition according to an example of the present invention can be added to various fuels such as gasoline, diesel, and heavy oil to improve combustion efficiency during fuel combustion and at the same time significantly reduce the generation of air pollutants such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NOx). In addition, a fuel additive composition according to an example of the present invention can inhibit oxidation of bio-heavy oil or a mixed heavy oil of petroleum-based heavy oil and bio-heavy oil and significantly improve the storage stability. Therefore, a fuel additive composition according to an example of the present invention can contribute to the prevention of global warming and air pollution.
도 1은 본 발명의 실시예에서 아세틸아세토네이트 계열의 다양한 유용성 금속화합물(Oil soluble metallic compound)을 벙커C유에 첨가하여 연료유를 제조하고, 보일러에서 연소시켰을 때 배출되는 분진 농도를 측정한 결과이다.Figure 1 shows the results of measuring the concentration of dust emitted when fuel oil was manufactured by adding various oil soluble metallic compounds of the acetylacetonate series to bunker C oil and burning it in a boiler in an embodiment of the present invention.
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 protection scope of the present invention.
1. 연소촉진제로 사용되는 유용성 금속화합물(Oil soluble metallic compound)의 분진(Dust) 저감 성능 탐색1. Exploration of dust reduction performance of oil soluble metallic compound used as combustion accelerator
아세틸아세토네이트 계열의 다양한 유용성 금속화합물(Oil soluble metallic compound)을 벙커C유(유황 1 wt % 포함)에 30 ppm(금속 성분 기준)의 비율로 첨가하여 연료유를 제조하였다. 이후, 연료유를 0.2톤/시간 규모의 실험용 보일러에서 연소시킨 후, 분진 배출 농도를 측정하였다. 도 1은 본 발명의 실시예에서 아세틸아세토네이트 계열의 다양한 유용성 금속화합물(Oil soluble metallic compound)을 벙커C유에 첨가하여 연료유를 제조하고, 보일러에서 연소시켰을 때 배출되는 분진 농도를 측정한 결과이다. 도 1의 X축에 기재된 A, B, C, D 및 E가 의미하는 바는 다음과 같다.Various oil soluble metallic compounds of the acetylacetonate series were added to bunker C oil (containing 1 wt % sulfur) at a ratio of 30 ppm (based on metal component) to manufacture fuel oil. Thereafter, the fuel oil was combusted in an experimental boiler of 0.2 ton/hour scale, and the dust emission concentration was measured. Fig. 1 is a result of measuring the dust concentration emitted when fuel oil was manufactured by adding various oil soluble metallic compounds of the acetylacetonate series to bunker C oil and combusted in a boiler in an example of the present invention. The meanings of A, B, C, D, and E described on the X-axis of Fig. 1 are as follows.
* A : 무첨가(No Additive)* A: No Additive
* B : 철(Ⅲ)아세틸아세토네이트[Iron(Ⅲ) acetylacetonate; CAS 등록번호 : 14024-18-1]* B: Iron(Ⅲ) acetylacetonate [CAS registration number: 14024-18-1]
* C : 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1)* C: Calcium acetylacetonate hydrate (CAS registration number: 345909-31-1)
* D : 망간(Ⅱ)아세틸아세토네이트[Manganese(II) acetylacetonate; CAS 등록번호 : 14024-58-9]* D: Manganese(II) acetylacetonate [Manganese(II) acetylacetonate; CAS registration number: 14024-58-9]
* E : 마그네슘아세틸아세토네이트 이수화물(Magnesium acetylacetonate dihydrate; CAS 등록번호 : 68488-07-3)* E: Magnesium acetylacetonate dihydrate (CAS registration number: 68488-07-3)
도 1에서 보이는 바와 같이 아세틸아세토네이트 계열의 다양한 유용성 금속화합물(Oil soluble metallic compound) 중 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1)은 다른 유용성 금속화합물(Oil soluble metallic compound)에 비해 배출되는 분진 농도를 현저하게 감소시켰다.As shown in Figure 1, among various oil-soluble metallic compounds of the acetylacetonate series, calcium acetylacetonate hydrate (CAS registration number: 345909-31-1) significantly reduced the concentration of emitted dust compared to other oil-soluble metallic compounds.
2. 산화방지제의 산화 안정 성능 탐색2. Exploration of oxidation stability performance of antioxidants
다양한 산화방지제를 바이오디젤에 3%(w/v)의 양으로 첨가한 후 DIN EN 14112:2003 시험방법(method for the determination of oxidation stability of fatty acid methylesters)으로 가속조건(110℃)에서 산화안정도(Oxidation stability)를 측정하였다. 하기 표 1에 산화방지제의 종류에 따른 바이오디젤의 산화안정도 측정 결과를 정리하였다.After adding various antioxidants to biodiesel in an amount of 3% (w/v), oxidation stability was measured under accelerated conditions (110°C) using the DIN EN 14112:2003 test method (method for the determination of oxidation stability of fatty acid methylesters). Table 1 below summarizes the results of measuring the oxidation stability of biodiesel according to the type of antioxidant.
(octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate; CAS No. : 125643-61-0)Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate
(octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate; CAS No.: 125643-61-0)
(Butylated hydroxytoluene; CAS No. : 128-37-0)Butylated hydroxytoluene
(Butylated hydroxytoluene; CAS No.: 128-37-0)
(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0)tert-butylhydroquinone
(tert-Butylhydroquinone; CAS registration number: 1948-33-0)
상기 표에서 보이는 바와 같이 tert-부틸하이드로퀴논(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0)은 다른 산화방지제에 비해 바이오디젤의 산화안정도를 현저하게 개선하였다.As shown in the table above, tert-Butylhydroquinone (CAS registration number: 1948-33-0) significantly improved the oxidation stability of biodiesel compared to other antioxidants.
3. 연료첨가제 조성물의 제조3. Preparation of fuel additive composition
제조예 1.Manufacturing example 1.
tert-부틸하이드로퀴논(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0) 12 중량부, 칼슘석유술폰산염(Calcium petroleum sulfonate; CAS 등록번호 : 61789-86-4) 8 중량부, 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1) 22 중량부, 과염기성 칼슘석유술폰산염(Overbased calcium petroleum sulfonate; CAS 등록번호 : 68783-96-0) 17 중량부 및 솔비탄모노라우레이트(Sorbitan monolaurate; CAS 등록번호 : 1338-39-2) 32 중량부 및 2-에틸헥실 질산염(2-Ethylhexyl nitrate; CAS 등록번호 : 27247-96-7) 9 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.12 parts by weight of tert-Butylhydroquinone (CAS Registry Number: 1948-33-0), 8 parts by weight of Calcium petroleum sulfonate (CAS Registry Number: 61789-86-4), 22 parts by weight of Calcium acetylacetonate hydrate (CAS Registry Number: 345909-31-1), 17 parts by weight of overbased calcium petroleum sulfonate (CAS Registry Number: 68783-96-0), and 32 parts by weight of Sorbitan monolaurate (CAS Registry Number: 1338-39-2) and 2-Ethylhexyl nitrate (CAS Registry Number: 27247-96-7) was uniformly mixed to prepare a fuel additive composition.
제조예 2.Manufacturing example 2.
tert-부틸하이드로퀴논(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0) 17 중량부, 칼슘석유술폰산염(Calcium petroleum sulfonate; CAS 등록번호 : 61789-86-4) 13 중량부, 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1) 28 중량부, 과염기성 칼슘석유술폰산염(Overbased calcium petroleum sulfonate; CAS 등록번호 : 68783-96-0) 12 중량부 및 솔비탄모노라우레이트(Sorbitan monolaurate; CAS 등록번호 : 1338-39-2) 25 중량부 및 2-에틸헥실 질산염(2-Ethylhexyl nitrate; CAS 등록번호 : 27247-96-7) 5 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.17 parts by weight of tert-Butylhydroquinone (CAS Registry Number: 1948-33-0), 13 parts by weight of Calcium petroleum sulfonate (CAS Registry Number: 61789-86-4), 28 parts by weight of Calcium acetylacetonate hydrate (CAS Registry Number: 345909-31-1), 12 parts by weight of overbased calcium petroleum sulfonate (CAS Registry Number: 68783-96-0), and 25 parts by weight of Sorbitan monolaurate (CAS Registry Number: 1338-39-2) and 2-Ethylhexyl nitrate (CAS Registry Number: 27247-96-7) was uniformly mixed to prepare a fuel additive composition.
제조예 3.Manufacturing example 3.
tert-부틸하이드로퀴논(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0) 15 중량부, 칼슘석유술폰산염(Calcium petroleum sulfonate; CAS 등록번호 : 61789-86-4) 10 중량부, 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1) 25 중량부, 과염기성 칼슘석유술폰산염(Overbased calcium petroleum sulfonate; CAS 등록번호 : 68783-96-0) 15 중량부 및 솔비탄모노라우레이트(Sorbitan monolaurate; CAS 등록번호 : 1338-39-2) 27 중량부 및 2-에틸헥실 질산염(2-Ethylhexyl nitrate; CAS 등록번호 : 27247-96-7) 8 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.15 parts by weight of tert-Butylhydroquinone (CAS Registry Number: 1948-33-0), 10 parts by weight of Calcium petroleum sulfonate (CAS Registry Number: 61789-86-4), 25 parts by weight of Calcium acetylacetonate hydrate (CAS Registry Number: 345909-31-1), 15 parts by weight of overbased calcium petroleum sulfonate (CAS Registry Number: 68783-96-0), and 27 parts by weight of Sorbitan monolaurate (CAS Registry Number: 1338-39-2) and 2-Ethylhexyl nitrate (CAS Registry Number: 27247-96-7) was uniformly mixed to prepare a fuel additive composition.
비교제조예 1.Comparative manufacturing example 1.
tert-부틸하이드로퀴논(tert-Butylhydroquinone; CAS 등록번호 : 1948-33-0) 15 중량부, 칼슘석유술폰산염(Calcium petroleum sulfonate; CAS 등록번호 : 61789-86-4) 10 중량부, 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1) 25 중량부, 과염기성 칼슘석유술폰산염(Overbased calcium petroleum sulfonate; CAS 등록번호 : 68783-96-0) 15 중량부 및 솔비탄모노라우레이트(Sorbitan monolaurate; CAS 등록번호 : 1338-39-2) 35 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.A fuel additive composition was prepared by uniformly mixing 15 parts by weight of tert-butylhydroquinone (CAS Registry Number: 1948-33-0), 10 parts by weight of calcium petroleum sulfonate (CAS Registry Number: 61789-86-4), 25 parts by weight of calcium acetylacetonate hydrate (CAS Registry Number: 345909-31-1), 15 parts by weight of overbased calcium petroleum sulfonate (CAS Registry Number: 68783-96-0), and 35 parts by weight of sorbitan monolaurate (CAS Registry Number: 1338-39-2).
비교제조예 2.Comparative manufacturing example 2.
2-에틸헥실 질산염(2-Ethylhexyl nitrate; CAS 등록번호 : 27247-96-7) 15 중량부, 칼슘석유술폰산염(Calcium petroleum sulfonate; CAS 등록번호 : 61789-86-4) 10 중량부, 칼슘아세틸아세토네이트 수화물(Calcium acetylacetonate hydrate; CAS 등록번호 : 345909-31-1) 25 중량부, 과염기성 칼슘석유술폰산염(Overbased calcium petroleum sulfonate; CAS 등록번호 : 68783-96-0) 15 중량부 및 솔비탄모노라우레이트(Sorbitan monolaurate; CAS 등록번호 : 1338-39-2) 35 중량부를 균일하게 혼합하여 연료첨가제 조성물을 제조하였다.A fuel additive composition was prepared by uniformly mixing 15 parts by weight of 2-ethylhexyl nitrate (CAS Registry Number: 27247-96-7), 10 parts by weight of calcium petroleum sulfonate (CAS Registry Number: 61789-86-4), 25 parts by weight of calcium acetylacetonate hydrate (CAS Registry Number: 345909-31-1), 15 parts by weight of overbased calcium petroleum sulfonate (CAS Registry Number: 68783-96-0), and 35 parts by weight of sorbitan monolaurate (CAS Registry Number: 1338-39-2).
4. 선박용 엔진에서의 연소 시험4. Combustion tests in marine engines
중유에 연료첨가제 조성물을 0.025%(v/v)의 양으로 첨가하여 연료유를 제조하고, 선박용 엔진( 제작자 : STX 엔진; 모델 : MAN B&W 51-23/30H; POWER : 650 KW; SPEED : 720 rpm)에서 연소 시험을 진행한 후, 연료첨가제 조성물의 미세입자(particulate matter, PM), 이산화탄소(CO2), 탄화수소(HC), 질소산화물(NOx) 저감 효과를 ISO 8178-2 시험방법(Reciprocating internal combustion engines-Exhaust emission measurement-Part 2: Measurement of gaseous and particulate exhaust emissions under field conditions)으로 측정하였다.Fuel oil was manufactured by adding a fuel additive composition to heavy oil in an amount of 0.025% (v/v), and a combustion test was conducted in a marine engine (Manufacturer: STX Engine; Model: MAN B&W 51-23/30H; POWER: 650 KW; SPEED: 720 rpm). Then, the reduction effect of the fuel additive composition on particulate matter (PM), carbon dioxide (CO2 ), hydrocarbons (HC), and nitrogen oxides (NOx) was measured using the ISO 8178-2 test method (Reciprocating internal combustion engines-Exhaust emission measurement-Part 2: Measurement of gaseous and particulate exhaust emissions under field conditions).
하기 표 2에 중유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 선박용 엔진에서 연소 시험을 진행하였을 때, 미세입자(particulate matter, PM) 배출 농도 측정 결과를 정리하였다. 하기 표 3에 중유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 선박용 엔진에서 연소 시험을 진행하였을 때, 이산화탄소(CO2) 배출 농도 측정 결과를 정리하였다. 하기 표 4에 중유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 선박용 엔진에서 연소 시험을 진행하였을 때, 탄화수소(HC) 배출 농도 측정 결과를 정리하였다. 하기 표 5에 중유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 선박용 엔진에서 연소 시험을 진행하였을 때, 질소산화물(NOx) 배출 농도 측정 결과를 정리하였다.The results of measuring the concentration of particulate matter (PM) emissions when fuel oil was manufactured by adding a fuel additive composition to heavy oil and a combustion test was performed in a marine engine are summarized in Table 2 below. The results of measuring the concentration of carbon dioxide (CO2 ) emissions when fuel oil was manufactured by adding a fuel additive composition to heavy oil and a combustion test was performed in a marine engine are summarized in Table 3 below. The results of measuring the concentration of hydrocarbon (HC) emissions when fuel oil was manufactured by adding a fuel additive composition to heavy oil and a combustion test was performed in a marine engine are summarized in Table 4 below. The results of measuring the concentration of nitrogen oxide (NOx) emissions when fuel oil was manufactured by adding a fuel additive composition to heavy oil and a combustion test was performed in a marine engine are summarized in Table 5 below.
(저감율 : 36.8%)573.8
(Reduction rate: 36.8%)
(저감율 : 44.5%)445.9
(Reduction rate: 44.5%)
(저감율 : 47.1%)237.5
(Reduction rate: 47.1%)
(저감율 : 37.5%)567.4
(Reduction rate: 37.5%)
(저감율 : 45.1%)441.1
(Reduction rate: 45.1%)
(저감율 : 47.9%)233.9
(Reduction rate: 47.9%)
(저감율 : 39.3%)551.1
(Reduction rate: 39.3%)
(저감율 : 46%)433.9
(Reduction rate: 46%)
(저감율 :49%)228.9
(Reduction rate: 49%)
(저감율 : 10.33%)814.1
(Reduction rate: 10.33%)
(저감율 : 18.49%)654.9
(Reduction rate: 18.49%)
(저감율 : 20.78%)355.6
(Reduction rate: 20.78%)
(저감율 : 11.09%)807.2
(Reduction rate: 11.09%)
(저감율 : 19.12%)649.9
(Reduction rate: 19.12%)
(저감율 : 22.15%)349.5
(Reduction rate: 22.15%)
(엔진 부하 50% 조건)Carbon dioxide (CO2 ) emission concentration (%)
(50% engine load condition)
(엔진 부하 50% 조건)Hydrocarbon (HC) emission concentration (ppm)
(50% engine load condition)
(엔진 부하 50% 조건)Nitrogen oxide (NOx) emission concentration (ppm)
(50% engine load condition)
5. 휘발유 내연기관에서의 연소 시험5. Combustion test in gasoline internal combustion engine
휘발유에 연료첨가제 조성물을 0.1%(v/v)의 양으로 첨가하여 연료유를 제조하고, 휘발유 차량용 엔진에서 연소 시험을 진행한 후, 연료첨가제 조성물의 일산화탄소(CO), 탄화수소(HC), 질소산화물(NOx) 저감 효과를 GB/T 19233-2008 시험방법(Chinese Standard : Measurement methods of fuel consumption for light-duty vehicles) 및 GB 18352.3-2005 시험방법[Chinese Standard : Limits and measurement methods for emissions from light-duty vehicles (III, IV)]으로 측정하였다.Fuel oil was manufactured by adding a fuel additive composition to gasoline in an amount of 0.1% (v/v), and a combustion test was conducted in a gasoline vehicle engine. The reduction effects of the fuel additive composition on carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NOx) were measured according to the test method of GB/T 19233-2008 (Chinese Standard: Measurement methods of fuel consumption for light-duty vehicles) and the test method of GB 18352.3-2005 [Chinese Standard: Limits and measurement methods for emissions from light-duty vehicles (III, IV)].
하기 표 6에 휘발유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 휘발유 차량용 엔진에서에서 연소 시험을 진행하였을 때, 일산화탄소(CO) 배출량 측정 결과를 정리하였다. 하기 표 7에 휘발유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 휘발유 차량용 엔진에서 연소 시험을 진행하였을 때, 탄화수소(HC) 배출량 측정 결과를 정리하였다. 하기 표 8에 휘발유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 휘발유 차량용 엔진에서 연소 시험을 진행하였을 때, 질소산화물(NOx) 배출량 측정 결과를 정리하였다.The results of measuring carbon monoxide (CO) emissions when fuel oil was manufactured by adding a fuel additive composition to gasoline and a combustion test was performed in a gasoline vehicle engine are summarized in Table 6 below. The results of measuring hydrocarbon (HC) emissions when fuel oil was manufactured by adding a fuel additive composition to gasoline and a combustion test was performed in a gasoline vehicle engine are summarized in Table 7 below. The results of measuring nitrogen oxide (NOx) emissions when fuel oil was manufactured by adding a fuel additive composition to gasoline and a combustion test was performed in a gasoline vehicle engine are summarized in Table 8 below.
5. 경유 내연기관에서의 연소 시험5. Combustion test in a diesel internal combustion engine
경유에 연료첨가제 조성물을 0.1%(v/v)의 양으로 첨가하여 연료유를 제조하고, 경유 차량용 엔진에서 연소 시험을 진행한 후, 연료첨가제 조성물의 미세입자(particulate matter, PM), 일산화탄소(CO), 탄화수소(HC), 질소산화물(NOx) 저감 효과를 GB 17691-2005 시험방법[Chinese Standard : Limits and measurement methods for exhaust pollutants from compression ignition and gas fuelled positive ignition engines of vehicles (III IV V)] 및 GB/T 17692-1999 시험방법(Chinese Standard : Measurement methods of net power for automotive engines)으로 측정하였다.A fuel additive composition was added to kerosene at an amount of 0.1% (v/v) to manufacture fuel oil, and a combustion test was conducted in a kerosene vehicle engine. The reduction effects of the fuel additive composition on particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NOx) were measured according to the GB 17691-2005 test method [Chinese Standard: Limits and measurement methods for exhaust pollutants from compression ignition and gas-fuelled positive ignition engines of vehicles (III IV V)] and the GB/T 17692-1999 test method (Chinese Standard: Measurement methods of net power for automotive engines).
하기 표 9에 경유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 경유차량용 엔진에서에서 연소 시험을 진행하였을 때, 미세입자(particulate matter, PM) 배출량 측정 결과를 정리하였다. 하기 표 10에 경유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 경유 차량용 엔진에서에서 연소 시험을 진행하였을 때, 일산화탄소(CO) 배출량 측정 결과를 정리하였다. 하기 표 11에 경유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 경유 차량용 엔진에서 연소 시험을 진행하였을 때, 탄화수소(HC) 배출량 측정 결과를 정리하였다. 하기 표 12에 경유에 연료첨가제 조성물을 첨가하여 연료유를 제조하고 경유 차량용 엔진에서 연소 시험을 진행하였을 때, 질소산화물(NOx) 배출량 측정 결과를 정리하였다.The results of measuring particulate matter (PM) emissions when fuel oil was manufactured by adding a fuel additive composition to kerosene, and a combustion test was performed in a diesel vehicle engine are summarized in Table 9 below. The results of measuring carbon monoxide (CO) emissions when fuel oil was manufactured by adding a fuel additive composition to kerosene, and a combustion test was performed in a diesel vehicle engine are summarized in Table 10 below. The results of measuring hydrocarbon (HC) emissions when fuel oil was manufactured by adding a fuel additive composition to kerosene, and a combustion test was performed in a diesel vehicle engine are summarized in Table 11 below. The results of measuring nitrogen oxide (NOx) emissions when fuel oil was manufactured by adding a fuel additive composition to kerosene, and a combustion test was performed in a diesel vehicle engine are summarized in Table 12 below.
상기 표 2 내지 표 12에서 보이는 바와 같이 제조예 1 내지 제조예 3에서 제조한 연료첨가제 조성물은 휘발유, 경유, 중유 등과 같은 다양한 연료에 첨가되어 연료 연소시 연소 효율을 향상시키고 동시에 미세입자(particulate matter, PM), 일산화탄소(CO), 탄화수소(HC), 질소산화물(NOx) 등과 같은 대기 오염물질의 발생을 크게 감소시켰다. 특히, 제조예 1 내지 제조예 3에서 제조한 연료첨가제 조성물의 대기 오염물질 저감 효과는 비교제조예 1 및 비교제조예 2에서 제조한 연료첨가제 조성물에 비해 현저하게 높은 것으로 확인되었다.As shown in Tables 2 to 12 above, the fuel additive compositions manufactured in Manufacturing Examples 1 to 3 were added to various fuels such as gasoline, diesel, and heavy oil to improve combustion efficiency during fuel combustion and at the same time significantly reduce the emission of air pollutants such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NOx). In particular, the air pollutant reduction effect of the fuel additive compositions manufactured in Manufacturing Examples 1 to 3 was confirmed to be significantly higher than that of the fuel additive compositions manufactured in Comparative Manufacturing Examples 1 and 2.
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-described embodiments, but the protection scope of the present invention is not necessarily limited thereto, and various modifications may be made within a scope that does not depart from the scope and spirit of the present invention. Accordingly, the protection scope of the present invention should be interpreted to include all embodiments falling within the scope of the patent claims attached to the present invention.
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|---|---|
| KR (1) | KR102812708B1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20090069179A (en)* | 2006-10-24 | 2009-06-29 | 켐트라 코포레이션 | Soluble oils with overbased sulfonate additives |
| WO2011014424A1 (en)* | 2009-07-31 | 2011-02-03 | Exxonmobil Research And Engineering Company | Biodiesel and biodiesel blend fuels |
| KR101071204B1 (en)* | 2011-03-08 | 2011-10-10 | 이영서 | Fuel additive for heavy oil and fuel oil comprising the same |
| CN106244263A (en)* | 2016-08-23 | 2016-12-21 | 广西东奇能源技术有限公司 | Multifunctional fuel oil additive |
| KR101836946B1 (en)* | 2015-09-17 | 2018-04-19 | 이영서 | Fuel additive for reducing greenhouse gases, NOx and particulate matter |
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| KR20240065699A (en)* | 2022-11-07 | 2024-05-14 | 이영서 | Fuel additives composition for Bio-heavy oil and use of the same |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090069179A (en)* | 2006-10-24 | 2009-06-29 | 켐트라 코포레이션 | Soluble oils with overbased sulfonate additives |
| WO2011014424A1 (en)* | 2009-07-31 | 2011-02-03 | Exxonmobil Research And Engineering Company | Biodiesel and biodiesel blend fuels |
| KR101071204B1 (en)* | 2011-03-08 | 2011-10-10 | 이영서 | Fuel additive for heavy oil and fuel oil comprising the same |
| KR101836946B1 (en)* | 2015-09-17 | 2018-04-19 | 이영서 | Fuel additive for reducing greenhouse gases, NOx and particulate matter |
| CN106244263A (en)* | 2016-08-23 | 2016-12-21 | 广西东奇能源技术有限公司 | Multifunctional fuel oil additive |
| KR102615558B1 (en)* | 2017-02-21 | 2023-12-18 | 교도유시 가부시끼가이샤 | Lubricant composition for reducer and reducer |
| KR20240065699A (en)* | 2022-11-07 | 2024-05-14 | 이영서 | Fuel additives composition for Bio-heavy oil and use of the same |
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