KR100566107B1 - Removal method of free fatty acid in wasted edible oil - Google Patents
Removal method of free fatty acid in wasted edible oil Download PDFInfo
- Publication number
- KR100566107B1 KR100566107B1 KR1020030022078A KR20030022078A KR100566107B1 KR 100566107 B1 KR100566107 B1 KR 100566107B1 KR 1020030022078 A KR1020030022078 A KR 1020030022078A KR 20030022078 A KR20030022078 A KR 20030022078A KR 100566107 B1 KR100566107 B1 KR 100566107B1
- Authority
- KR
- South Korea
- Prior art keywords
- free fatty
- cooking oil
- oil
- fatty acids
- fatty acid
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
Abstract
본 발명은 폐식용유중의 유리지방산 제거방법에 관한 것으로 보다 상세하게는 폐식용유에 함유된 유리지방산을 불균질계 무기 고체 산촉매(heterogeneous solid acid catalyst)를 이용하여 폐식용유중의 유리지방산을 제거하는 방법에 관한 것이다.The present invention relates to a method for removing free fatty acids from waste cooking oil, and more particularly, to remove free fatty acids from waste cooking oil using a heterogeneous inorganic solid acid catalyst. It is about a method.
본 발명은 바이오디젤유의 제조의 원료로 사용할 수 있도록 폐식용유중에 함유된 유리지방산을 불균질계 무기 고체 산촉매를 이용하여 제거할 수 있는 폐식용유중의 유리지방산 제거방법 제공을 목적으로 한다.An object of the present invention is to provide a method for removing free fatty acids in used cooking oil which can remove free fatty acids contained in used cooking oil using a heterogeneous inorganic solid acid catalyst so as to be used as a raw material for producing biodiesel oil.
본 발명의 폐식용유중의 유리지방산 제거방법은 폐식용중의 유리지방산 제거에 있어서, 불균질계 무기 고체 산촉매하에서 알콜과 유리지방산을 함유한 폐식용유를 반응시키는 단계를 포함한다.The method for removing free fatty acids in used cooking oil of the present invention includes the step of reacting the used cooking oil containing alcohol and free fatty acids under a heterogeneous inorganic solid acid catalyst in removing free fatty acids in used cooking oil.
Description
본 발명은 폐식용유중의 유리지방산 제거방법에 관한 것으로 보다 상세하게는 불균질계 무기 고체산 촉매(heterogeneous inorganic solid acid catalyst)를 이용하여 폐식용유중의 유리지방산을 제거하는 방법에 관한 것이다.The present invention relates to a method for removing free fatty acids in waste cooking oil, and more particularly, to a method for removing free fatty acids in waste cooking oil by using a heterogeneous inorganic solid acid catalyst.
산업이 발전함에 따라 디젤엔진을 포함하는 산업기계들이 증가하고, 차량이 생활의 필수품이 되면서 전세계적으로 차량 생산의 증가에 따라 이들의 원료로 사용되고 있는 디젤유에 대한 소비도 증가하고 있다. As the industry develops, industrial machinery including diesel engines increases, and as vehicles become necessities of life, consumption of diesel oil, which is used as their raw material, increases as vehicle production increases worldwide.
디젤유는 원유로부터 얻어지는 여러 가지 연료 중에서 연비가 좋고, 가격이 저렴하며, 이산화탄소(CO2) 저감 측면에 대해 장점을 가지는 있다. 그러나 이러한 장점이 있는 반면 원유로부터 얻어지는 다른 연료에 비해 연소 후 대기오염 물질이 많이 발생하는 문제가 있다.Diesel oil has an advantage in terms of fuel efficiency, low cost, and carbon dioxide (CO 2 ) reduction among various fuels obtained from crude oil. However, while having these advantages, there is a problem that a lot of air pollutants are generated after combustion compared to other fuels obtained from crude oil.
이러한 문제점을 해결하기 위해 디젤유와 물성이 유사하며, 경제적인 비용 측면에서도 우수하고, 대기오염을 방지할 수 있는 대체 연료에 대한 다각적인 연구가 이루어지고 있다. 이러한 연구의 결과로 디젤유와 물성이 비슷하면서도 대기오염 발생을 현저히 감소할 수 있고, 나아가 CO2 저감 효과가 큰 자연 순환형 에너지인 바이오디젤유에 대하여 많은 연구가 이루어지고 있다.In order to solve this problem, various studies have been conducted on alternative fuels having similar properties to diesel oil, having excellent economical cost, and preventing air pollution. As a result of this study, much research has been conducted on biodiesel oil, which is a natural circulating energy having similar physical properties to diesel oil, but which can significantly reduce the generation of air pollution and have a large effect of reducing CO 2 .
바이오디젤유는 식물성 기름, 동물성 지방과 같은 유지 또는 재생가능한 폐식용유를 산 촉매 또는 알카리 촉매 존재 하에서 알콜과 반응하여 생성되는 에스테르화 기름이다.Biodiesel oil is an esterified oil produced by reacting a fat or renewable waste cooking oil such as vegetable oil or animal fat with alcohol in the presence of an acid catalyst or an alkali catalyst.
바이오디젤유는 차량의 연료에 사용하는 경유와 물성이 유사하여, 경유와 혼합하여 사용하거나 또는 경유를 대체하여 디젤엔진에 사용할 수 있다.Biodiesel oil has similar properties to diesel fuel used in vehicle fuel, and can be used in combination with diesel fuel or used in diesel engines in place of diesel fuel.
바이오디젤의 생산공정은 순수한 식용유와 같은 식물성 유지를 바이오디젤유의 원료로 이용하고 있다. 순수한 식용유는 바이오디젤유의 원료로서 좋지만 바이오디젤유의 제조시 순수한 식용유의 비용이 많이 소요된다. 즉, 바이오디젤유은 위와 같은 장점에 비해 생산단가가 기존의 경유 보다 높은 문제가 있다. Biodiesel production process uses vegetable oils such as pure cooking oil as raw materials for biodiesel oil. Pure cooking oil is good as a raw material of biodiesel oil, but the cost of pure cooking oil is high in producing biodiesel oil. In other words, biodiesel oil has a higher production cost than conventional diesel oil as compared to the above advantages.
따라서 바이오디젤유의 생산비용을 낮추기 위해서는 순수한 식용유 보다 비용이 훨씬 저렴한 폐식용유를 원료로 사용하는 바이오디젤유에 대한 필요성이 대두되고 있다. Therefore, in order to lower the production cost of biodiesel oil, there is a need for biodiesel oil using waste cooking oil, which is much cheaper than pure cooking oil, as a raw material.
바이오디젤유의 원료 물질에 수분과 유리지방산의 함량이 많으면 바이오디젤유 생산에 알칼리 촉매를 사용하는 경우 촉매가 쉽게 비활성화될 수 있고, 수분에 의해 가수분해가 일어날 수 있다. 그리고 유리지방산과 알칼리 촉매가 결합하여 생 성된 금속염에 의해 가수분해 반응이 더욱 촉진되게 된다. 또한, 바이오디젤유를 포함한 생성물에 금속염이 많이 생성되면 바이오디젤유로부터 이의 분리, 정제가 어려워 많은 비용과 시간이 소요되므로 바이오디젤유의 생산성이 감소하는 문제가 있다.If the raw material of biodiesel oil contains a large amount of water and free fatty acids, the catalyst may be easily deactivated when the alkali catalyst is used for biodiesel production, and hydrolysis may occur by moisture. In addition, the hydrolysis reaction is further promoted by the metal salt generated by combining the free fatty acid and the alkali catalyst. In addition, when a large number of metal salts are generated in a product including biodiesel oil, it is difficult to separate and purify the biodiesel oil from the biodiesel oil, and thus, a large cost and time are required, thereby reducing productivity of the biodiesel oil.
결국 이러한 문제를 해결하기 위해 폐식용유를 이용한 바이오디젤유의 제조시 폐식용유에 함유되어 있는 유리지방산의 함량을 낮추어야 하는 문제가 있다.As a result, in order to solve such a problem, there is a problem of lowering the content of free fatty acids contained in the waste cooking oil when preparing biodiesel oil using the waste cooking oil.
본 발명과 관련된 종래기술로서 미국 특허 제 4,363,590호, 제 4,608,202호 등에 대두유, 평지유, 옥수수유, 우지 등을 원료로 하여 바이오디젤유를 생산하는 방법이 기재되어 있다. 그러나 위의 특허들은 바이오다젤유의 원료가 폐식용유가 아니라, 순수한 유지를 이용한 바이오디젤유의 제조에 대한 내용이다. 또한 한국공개특허 제1999-0016815호(폐식용유를 이용한 자동차 연료 제조방법)는 유리지방산의 제거에 관한 내용은 없고, 단지 균일계 염기 촉매를 사용하여 1단계의 반응으로 폐식용유에서 바이오디젤유의 제조에 대한 내용이다. 또한 한국공개특허공보 제2002-0040693호(폐유 재생방법 및 그 장치)에서는 촉매에 대한 내용은 없이 흡착제를 이용하여 폐유로부터 유리지방산의 물리적인 제거방법이 제시되어 있으나, 유리지방산 제거 후 흡착제의 분리공정이 필요한 문제가 있다.As a related art of the present invention, U.S. Patent Nos. 4,363,590 and 4,608,202 and the like describe a method for producing biodiesel oil using soybean oil, rapeseed oil, corn oil, tallow and the like as raw materials. However, the above patents refer to the production of biodiesel oil using pure oil, not waste oil, as a raw material of biodiesel oil. In addition, Korean Patent Laid-Open Publication No. 1999-0016815 (Method for manufacturing automobile fuel using waste cooking oil) has no information on the removal of free fatty acids, and the production of biodiesel oil from waste cooking oil in a one-step reaction using a homogeneous base catalyst. This is about. In addition, Korean Laid-Open Patent Publication No. 2002-0040693 (Waste Oil Regeneration Method and Apparatus) discloses a method for physically removing free fatty acids from waste oil by using an adsorbent without a catalyst content. There is a problem that requires a process.
결국, 본원발명과 같이 불균질계 고체산 촉매를 사용하여 유리지방산을 제거하는 기술은 아직 실제적으로 확립되어 있지 않은 실정이다.As a result, a technique for removing free fatty acids using a heterogeneous solid acid catalyst as in the present invention has not been established yet.
본 발명은 바이오디젤유의 제조의 원료로 사용할 수 있도록 폐식용유중에 함유된 유리지방산을 불균질계 무기 고체 산촉매를 이용하여 제거할 수 있는 폐식용유중의 유리지방산 제거방법 제공을 목적으로 한다.An object of the present invention is to provide a method for removing free fatty acids in used cooking oil which can remove free fatty acids contained in used cooking oil using a heterogeneous inorganic solid acid catalyst so as to be used as a raw material for producing biodiesel oil.
즉, 본 발명은 하기의 반응식(1)과 같이 산촉매하에서 유리지방산과 알콜을 반응시켜 에스테르 물질과 수분을 생성하는 반응의 에스테르화법을 이용하여 폐식용유중에 함유된 유리지방산의 제거를 목적으로 한다.That is, the present invention aims to remove the free fatty acids contained in the waste cooking oil by using the esterification method of reacting the free fatty acid with the alcohol under an acid catalyst to produce an ester substance and water as shown in the following Reaction Formula (1).
RCOOH + R`OH → RCOOR` + H2O.....(1)RCOOH + R`OH → RCOOR` + H 2 O ..... (1)
유리지방산 + 알콜 → 에스테르 + 수분Free fatty acid + alcohol → ester + moisture
상기 식(1)에서 R은 탄소수가 C12∼C24인 알킬기이고, R'은 탄소수가 1∼4인 알킬기이다.In the formula (1) R is the number of carbon atoms is C 12 ~C 24 alkyl group, R 'is an alkyl group having the carbon number of 1 to 4.
한편 식(1)에서 유리지방산과 알콜의 반응에 의해 생성된 에스테르 물질은 바이오디젤유로 이용할 수 있다.
Meanwhile, the ester substance produced by the reaction of free fatty acid and alcohol in formula (1) can be used as biodiesel oil.
본 발명의 폐식용유중의 유리지방산 제거방법은 불균질계 무기 고체 산촉매하에서 알콜과 유리지방산을 함유하는 폐식용유를 반응시키는 단계를 포함한다.The free fatty acid removal method in the waste cooking oil of the present invention includes the step of reacting the waste cooking oil containing alcohol and free fatty acid under a heterogeneous inorganic solid acid catalyst.
본 발명에서 촉매는 불균질계 무기 고체 산촉매를 사용한다. 상기에서 언급한 바와 같이 염기성 촉매 존재하에서 유리지방산의 제거가 효율적이지 못하기 때문에 산촉매를 사용한다. 본 발명에서는 나중에 생성물이 생긴 후 생성물로부터 촉매의 분리가 용이하도록 불균질계 무기 고체 산촉매를 사용하는 것이 바람직하다.In the present invention, the catalyst uses a heterogeneous inorganic solid acid catalyst. As mentioned above, acid catalysts are used because the removal of free fatty acids in the presence of a basic catalyst is not efficient. In the present invention, it is preferable to use a heterogeneous inorganic solid acid catalyst in order to facilitate separation of the catalyst from the product after the product is formed later.
본 발명에서 사용할 수 있는 불균질계 무기 고체 산촉매의 일예로서 SO4 2-/ZrO2, 강산성 이온교환 수지인 Amberyst-15(Rohm&Haas Inc, USA), H3PW12O40, H4PMo12O40, H4SiW12O40, H4GeW12O40와 같은 헤테로폴리산(Heteropolyacid, HPA), HPA에서 수소 대신 세슘(Cs)이 일부 치환된 Cs-HPA(Cs2.5H0.5PW12O40), Cs-HPA(Cs2.5H0.5PW12O40)에서 Cs의 일부분이 니켈(Ni), 나트륨(Na), 칼륨(K), 루비듐(Rb), 프란슘(Fr)과 같은 1A족으로 치환된 치환염(Cs1∼2.4A0.1∼1.5H0.5PW12O40, A는 1A족 원소), SO4 2-/SiO2, 제올라이트(Zeolite) 중에서 선택된 어느 하나를 사용할 수 있다.As an example of the heterogeneous inorganic solid acid catalyst which can be used in the present invention, SO 4 2- / ZrO 2 , Amberyst-15 (Rohm & Haas Inc, USA), a strong acid ion exchange resin, H 3 PW 12 O 40 , H 4 PMo 12 O 40 , H 4 SiW 12 O 40 , Heteropolyacid (HPA), such as H 4 GeW 12 O 40 , Cs-HPA (Cs 2.5 H 0.5 PW 12 O 40 ) partially substituted with cesium (Cs) instead of hydrogen in HPA, Cs-HPA (Cs 2.5 H 0.5 PW 12 O 40 ) Substituted salt in which a part of Cs is substituted with group 1A such as nickel (Ni), sodium (Na), potassium (K), rubidium (Rb) and francium (Fr) (Cs 1 to 2.4 A 0.1 ˜1.5 H 0.5 PW 12 O 40 , A may be any one selected from Group 1A element), SO 4 2- / SiO 2 , and zeolite.
한편 HPA에서 세슘이 일부 치환된 Cs-HPA(Cs2.5H0.5PW12O40 )은 0.08M Cs2CO3(Sigma Aldrich) 수용액과 0.1M H3PW12O40 (일본무기화학공업주식회사) 수용액을 5:4의 몰비로 11시간 동안 교반한 후 증발 건조하여 얻을 수 있다. Meanwhile, Cs-HPA (Cs 2.5 H 0.5 PW 12 O 40 ) partially substituted with cesium in HPA was prepared using 0.08 M Cs 2 CO 3 (Sigma Aldrich) solution and 0.1 MH 3 PW 12 O 40 (Japan Inorganic Chemicals) solution. It can be obtained by stirring for 11 hours at a molar ratio of 5: 4 and then evaporating to dryness.
불균질계 무기 고체 산촉매는 폐식용유 중량에 대하여 5∼20% 사용할 수 있다. 불균질계 무기 고체 산촉매를 폐식용유 중량에 대해 5% 미만 사용하면 알콜과 폐식용유중의 유리지방산의 반응속도를 낮아지는 문제가 있고, 20% 초과 사용하면 촉매의 사용량 증가에 따른 뚜렷한 효과의 상승이 없으므로 불균질계 무기 고체 산촉매는 폐식용유 중량에 대하여 5∼20% 사용하는 것이 바람직하다.The heterogeneous inorganic solid acid catalyst may be used in an amount of 5 to 20% by weight of the waste cooking oil. If the heterogeneous inorganic solid acid catalyst is used less than 5% by weight of the waste cooking oil, the reaction rate of alcohol and free fatty acids in the waste cooking oil may be lowered. It is preferable that the heterogeneous inorganic solid acid catalyst be used in an amount of 5 to 20% based on the weight of the waste cooking oil.
본 발명에서 유리지방산을 함유하는 폐식용유와 알콜은 1:3~1:9의 몰비로 반응시킨다. 보다 바람직하게는 폐식용유와 알콜은 1:3~1:9의 몰비로 하여 60∼80℃에서 0.5∼12시간 동안 100∼600rpm으로 에스테르화 반응시킨다.In the present invention, the waste cooking oil containing the free fatty acid and the alcohol are reacted at a molar ratio of 1: 3 to 1: 9. More preferably, the waste cooking oil and alcohol are esterified at 100 to 600 rpm at a molar ratio of 1: 3 to 1: 9 at 60 to 80 ° C. for 0.5 to 12 hours.
본 발명에서 반응물인 알콜은 메탄올, 에탄올, 프로판올, 부탄올 중에서 선택된 어느 하나이거나 또는 둘 이상이 균일한 비로 혼합된 혼합물을 사용할 수 있다.In the present invention, the reactant alcohol may be any one selected from methanol, ethanol, propanol, butanol, or a mixture of two or more thereof in a uniform ratio.
본 발명에서 다양한 반응온도, 반응시간, 유지와 알콜의 반응몰비로 알콜과 유리지방산을 함유하는 폐식용유를 반응시켜 에스테르를 제조한바 페식용유와 알콜의 반응몰비가 1:3~1:9이고, 60~80℃에서 0.5~12시간 동안 100∼600rpm으로 반응시 에스테르의 수율이 좋다. 따라서 본 발명에서 폐식용유와 알콜은 1:3∼1:9의 몰비로 60∼80℃에서 0.5∼12시간 동안 100∼600rpm으로 에스테르화 반응시키는 것이 바람직하다.In the present invention, various reaction temperatures, reaction times, fats and oils and the reaction molar ratio of alcohol to the reaction of the waste cooking oil containing alcohol and free fatty acid to prepare the ester bar molar ratio of edible oil and alcohol is 1: 3 ~ 1: 9, The yield of the ester is good when the reaction is carried out at 60 to 80 ° C. for 100 to 600 rpm for 0.5 to 12 hours. Therefore, in the present invention, it is preferable that the waste cooking oil and alcohol are esterified at 100 to 600 rpm for 0.5 to 12 hours at 60 to 80 ° C. in a molar ratio of 1: 3 to 1: 9.
본 발명에서 폐식용유와 알콜의 에스테르화 반응이 종료되면 원심분리기를 이용하여 불균질계 무기 고체 산촉매를 분리한다. 그런 다음 생성물 중에 함유된 수분은 증발을 통해서 제거한다. 생성물중에서 수분을 제거하면 에스테르와 폐식용유의 주성분인 트리글리세세리드가 남는데 이를 정치법, 원심분리와 같은 공지의 방법으로 분리하여 에스테르를 분리한다. 에스테르를 분리한 폐식용유는 유리지방산이 함량이 현격히 낮아지게 되어 이를 바이오디젤유의 제조원료로 사용할 수 있다. In the present invention, when the esterification reaction of the waste cooking oil and alcohol is completed, a heterogeneous inorganic solid acid catalyst is separated using a centrifuge. The water contained in the product is then removed by evaporation. When water is removed from the product, esters and triglycerides, which are the main components of the waste cooking oil, remain, which are separated by known methods such as stationary methods and centrifugation to separate esters. The waste cooking oil separated from the ester has a significantly lower free fatty acid content, which can be used as a raw material for biodiesel oil.
에스테르를 분리한 후 에스테르화 반응에 의해 생성된 생성물의 산가를 측정함으로써 유리지방산의 감소여부를 측정한다.After the ester is separated, the free fatty acid is reduced by measuring the acid value of the product produced by the esterification reaction.
본 발명에서 산가는 적정법으로 에스테르를 분리한 폐식용유 속에 남아있는 유리지방산을 측정함으로써 산가를 평가한다. 생성물 10g의 시료를 취하여 벤젠 25ml와 에탄올 25ml의 혼합용액과 섞은 다음, 페놀프탈레인 지시약 한방울을 넣고 0.1N 수산화칼륨(KOH)으로 적정하여, 소요된 KOH양으로부터 산가를 계산한다.In the present invention, the acid value is evaluated by measuring the free fatty acid remaining in the waste cooking oil separated from the ester by a titration method. A sample of 10 g of the product is taken and mixed with a mixture of 25 ml of benzene and 25 ml of ethanol, a drop of phenolphthalein indicator is added, titrated with 0.1 N potassium hydroxide (KOH), and the acid value is calculated from the required amount of KOH.
한편 본 발명은 상기에서 언급한 방법으로 유리지방산을 제거한 폐식용유를 바이오디젤유의 제조원료로 사용할 수 있다.Meanwhile, the present invention can use waste cooking oil from which free fatty acids have been removed by the above-mentioned method as a raw material of biodiesel oil.
이하 본 발명을 다음의 실시예 및 시험예에 의하여 설명하고자 한다. 그러나 이들은 본 발명의 일실시예로서 이들에 의해 본 발명의 권리범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described by the following examples and test examples. However, these are not limited to the scope of the present invention by these as an embodiment of the present invention.
<실시예 1><Example 1>
폐식용유로서 4%의 유리지방산을 함유하고 있는 대두유(입수처:제일제당) 50g, 메탄올 2.2g 및 불균질계 무기 고체 산촉매로서 SO4 2-/ZrO2를 2.5∼10g 첨가하고 75℃에서 2시간 동안 300rpm의 교반속도로 다음 반응식(1)과 같이 반응시켰다.50 g of soybean oil containing 4% free fatty acid as waste oil (from Japan), 2.2 g of methanol and 2.5 to 10 g of SO 4 2- / ZrO 2 as a heterogeneous inorganic solid acid catalyst were added at 75 ° C. The reaction was carried out at the stirring speed of 300 rpm for the time as in the following Reaction (1).
RCOOH + R`OH → RCOOR` + H2O.....(1)RCOOH + R`OH → RCOOR` + H 2 O ..... (1)
유리지방산 + 알콜 → 에스테르 + 수분Free fatty acid + alcohol → ester + moisture
상기 식(1)에서 R은 탄소수가 C12∼C24인 알킬기이고, R'은 탄소수가 1∼4인 알킬기이다.In the formula (1) R is the number of carbon atoms is C 12 ~C 24 alkyl group, R 'is an alkyl group having the carbon number of 1 to 4.
반응종료 후 생성물을 원심분리하여 불균질계 무기 고체 산촉매와 에스테르를 차례로 분리하였다. 에스테르를 분리한 생성물 10g 시료를 벤젠 25ml와 에탄올 25ml의 혼합용액과 섞은 다음, 페놀프탈레인 지시약 한방울을 넣고 0.1N KOH로 적정하여, 소요된 KOH양으로부터 산가가 계산하였다. After completion of the reaction, the product was centrifuged to separate the heterogeneous inorganic solid acid catalyst and the ester sequentially. A 10 g sample of the separated product was mixed with a mixed solution of 25 ml of benzene and 25 ml of ethanol, a drop of phenolphthalein indicator was added thereto, titrated with 0.1 N KOH, and the acid value was calculated from the required amount of KOH.
한편 4%의 유리지방산을 함유하고 있는 대두유를 알콜과 반응시키기 전에 위와 같은 조건으로 미리 산가를 측정하였다. 4%의 유리지방산을 함유하고 있는 대두유의 상기 반응식(1)과 같은 반응 전후의 산가에 대해 하기의 식 (2)와 같이 유리지방산의 제거율을 측정하고 그 결과를 아래의 표 1에 나타내었다.On the other hand, the acid value of the soybean oil containing 4% free fatty acid was measured beforehand under the same conditions as before. Regarding the acid value before and after the reaction, such as the reaction formula (1) of soybean oil containing 4% free fatty acid, the removal rate of the free fatty acid was measured as shown in the following formula (2), and the results are shown in Table 1 below.
유리지방산 제거율(%) = ((A-B)/A×100)......(2)Free fatty acid removal rate (%) = ((A-B) / A × 100) ...... (2)
상기 식(2)에서 A는 4% 유리지방산을 함유하는 대두유의 산가이고, B는 반응 후 대두유의 산가이다.In Formula (2), A is the acid value of soybean oil containing 4% free fatty acid, and B is the acid value of soybean oil after the reaction.
한편 상기에서 사용한 불균질계 무기 고체 산촉매는 Zr(OH)4을 0.5M 황산에 5cc/g으로 담지하고, 1시간 동안 침전시킨 다음 여과한 후 150℃에서 6시간 동안 건조하고, 550℃ Air 분위기에서 3시간 동안 소성하여 제조한 것을 사용하였다.On the other hand, the heterogeneous inorganic solid acid catalyst used in the above was supported by Zr (OH) 4 in 0.5M sulfuric acid at 5cc / g, precipitated for 1 hour, filtered and dried at 150 ° C for 6 hours, and at 550 ° C air atmosphere. It was prepared by firing for 3 hours at.
표 1. 촉매 사용량에 따른 유리지방산의 제거율Table 1. Removal of Free Fatty Acids According to Catalyst Usage
<실시예 2><Example 2>
폐식용유로서 4%의 유리지방산을 함유하고 있는 대두유(입수처:제일제당) 50g, 메탄올 2.2g 및 불균질계 무기 고체 산촉매로서 Amberyst-15(Rohm&Haas Inc, USA)를 5∼10g 첨가하고 75℃에서 2시간 동안 300rpm의 교반속도로 실시예 1의 반응식(1)과 같이 반응시켰다.50 g of soybean oil containing 4% free fatty acid as waste oil (from Japan), 2.2 g of methanol and 5-10 g of Amberyst-15 (Rohm & Haas Inc, USA) as a heterogeneous inorganic solid acid catalyst were added at 75 ° C. The reaction was carried out as in Scheme 1 in Example 1 at a stirring speed of 300 rpm for 2 hours.
반응종료 후 생성물을 원심분리하여 불균질계 무기 고체 산촉매를 회수하고, 에스테르를 분리하였다. 에스테르를 분리한 생성물 10g 시료를 벤젠 25ml와 에탄올 25ml의 혼합용액과 섞은 다음, 페놀프탈레인 지시약 한방울을 넣고 0.1N KOH로 적정하여, 소요된 KOH양으로부터 산가가 계산하였다. After completion of the reaction, the product was centrifuged to recover a heterogeneous inorganic solid acid catalyst, and the ester was separated. A 10 g sample of the separated product was mixed with a mixed solution of 25 ml of benzene and 25 ml of ethanol, a drop of phenolphthalein indicator was added thereto, titrated with 0.1 N KOH, and the acid value was calculated from the required amount of KOH.
한편 4%의 유리지방산을 함유하고 있는 대두유를 알콜과 반응시키기 전에 위와 같은 조건으로 미리 산가를 측정하였다. 4%의 유리지방산을 함유하고 있는 대두유의 상기 반응식(1)과 같은 반응 전후의 산가에 대해 실시예 1의 식 (2)와 같이 유리지방산의 제거율을 측정하고 그 결과를 아래의 표 2에 나타내었다.On the other hand, the acid value of the soybean oil containing 4% free fatty acid was measured beforehand under the same conditions as before. For acid values before and after the reaction, such as the reaction formula (1) of soybean oil containing 4% free fatty acid, the removal rate of the free fatty acid was measured as shown in the formula (2) of Example 1, and the results are shown in Table 2 below. It was.
표 2. 촉매 사용량에 따른 유리지방산의 제거율Table 2. Removal Rate of Free Fatty Acids According to Catalyst Usage
*유리지방산제거율(%) = ((A-B)/A×100)*% Free fatty acid removal rate = ((A-B) / A × 100)
A: 4% 유리지방산을 함유하는 대두유의 산가A: Acid value of soybean oil containing 4% free fatty acid
B : 반응 후 대두유의 산가B: Acid value of soybean oil after reaction
본 발명에 의해 유리지방산의 함량을 낮아진 폐식용유는 이를 원료로 하여 바이오디젤유의 제조시 염기 촉매의 비활성화를 감소시켜 바이오디젤의 생산수율을 높일 뿐만 아니라 바이오디젤유의 생산단가를 낮출 수 있다.Waste cooking oil having a lower content of free fatty acids by the present invention can reduce the deactivation of the base catalyst during the production of biodiesel oil, thereby increasing the yield of biodiesel as well as lowering the production cost of biodiesel oil.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020030022078A KR100566107B1 (en) | 2003-04-08 | 2003-04-08 | Removal method of free fatty acid in wasted edible oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020030022078A KR100566107B1 (en) | 2003-04-08 | 2003-04-08 | Removal method of free fatty acid in wasted edible oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20040087625A KR20040087625A (en) | 2004-10-14 |
| KR100566107B1 true KR100566107B1 (en) | 2006-03-30 |
Family
ID=37369733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020030022078A KR100566107B1 (en) | 2003-04-08 | 2003-04-08 | Removal method of free fatty acid in wasted edible oil |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100566107B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101220326B1 (en) | 2010-12-22 | 2013-01-10 | 한국화학연구원 | Preparing method of Bio-diesel from bio-oils of high acid value using Acid-base catalyst combinations |
| KR20230174011A (en) | 2022-06-20 | 2023-12-27 | 주식회사 케이오에스 | Apparatus for esterification of fatty acid |
| KR20230174004A (en) | 2022-06-20 | 2023-12-27 | 주식회사 케이오에스 | Method for esterification of fatty acid |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100782127B1 (en) * | 2006-01-13 | 2007-12-05 | 한국에너지기술연구원 | Removing method of free fatty acid in oil using ionic liquid catalyst |
| US7951967B2 (en) | 2006-04-28 | 2011-05-31 | Sk Chemicals Co., Ltd. | Method and apparatus for preparing fatty acid alkyl ester using fatty acid |
| KR100798604B1 (en) * | 2006-09-18 | 2008-01-28 | 전남대학교산학협력단 | Removal method of free fatty acid in oil using heterogenous catalyst |
| KR100831072B1 (en) * | 2006-09-18 | 2008-05-20 | 전남대학교산학협력단 | Purification method of biodiesel using heterogenous catalyst |
| US20090183422A1 (en) * | 2008-01-18 | 2009-07-23 | Wysong Robert D | Process and system for preparation of bio-fuels |
| JP5380523B2 (en) | 2008-04-01 | 2014-01-08 | エスケー ケミカルズ カンパニー リミテッド | Method for producing fatty acid alkyl ester using fatty acid |
| KR101554607B1 (en) | 2008-11-07 | 2015-09-22 | 에스케이케미칼주식회사 | Method and apparatus for preparing fatty acid alkyl ester using fatty acid |
| KR102327852B1 (en) | 2013-07-22 | 2021-11-18 | 에스케이에코프라임 주식회사 | Method for preparing fatty acid alkyl ester using fat |
| JP6770554B2 (en) | 2018-07-23 | 2020-10-14 | 国立大学法人東京農工大学 | Biofuel manufacturing method |
| CN114452988B (en) * | 2021-12-31 | 2024-06-11 | 中国石油天然气股份有限公司 | Supported heteropolyacid nano catalyst and preparation method thereof and preparation method of aryl methyl stearate |
-
2003
- 2003-04-08 KR KR1020030022078A patent/KR100566107B1/en active IP Right Grant
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101220326B1 (en) | 2010-12-22 | 2013-01-10 | 한국화학연구원 | Preparing method of Bio-diesel from bio-oils of high acid value using Acid-base catalyst combinations |
| KR20230174011A (en) | 2022-06-20 | 2023-12-27 | 주식회사 케이오에스 | Apparatus for esterification of fatty acid |
| KR20230174004A (en) | 2022-06-20 | 2023-12-27 | 주식회사 케이오에스 | Method for esterification of fatty acid |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040087625A (en) | 2004-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4695411A (en) | Process for manufacturing a composition of fatty acid esters useful as gas oil substitute motor fuel with hydrated ethyl alcohol and the resultant esters composition | |
| de Lima et al. | Heterogeneous basic catalysts for biodiesel production | |
| KR100566107B1 (en) | Removal method of free fatty acid in wasted edible oil | |
| RU2428460C2 (en) | Hydrocarbon fuel obtaining method | |
| CA2634819C (en) | Process for the preparation of biodiesel | |
| AU2003290414B2 (en) | Improved process for preparing fatty acid alkylesters using as biodiesel | |
| EP2113019B1 (en) | Use of fuels or fuel additives based on triglycerides of modified structure | |
| US7741502B2 (en) | Method of manufacturing alcohol esters from triglycerides and alcohols using heterogeneous catalysts based on phosphate or an organophosphorous compound of a group 4 metal | |
| US20070004599A1 (en) | Process for the preparation of lubricants | |
| EP2049461B1 (en) | Process for the production of biodiesel | |
| US20090203092A1 (en) | Liquid Biofuel Mixture and Method and Device for Producing The Same | |
| CZ285119B6 (en) | Process for preparing esters from fats of natural origin | |
| CN101139328B (en) | Novel process for synthesizing epoxy aliphatic acid methyl ester | |
| Yatish et al. | Sodium phosphate synthesis through glycerol purification and its utilization for biodiesel production from dairy scum oil to economize production cost | |
| ES2194598B2 (en) | PROCEDURE FOR TRANSESTERIFICATION OF TRIGLYCERIDS WITH LOW MOLECULAR MONOALCOHOLES FOR OBTAINING LIGHT ALCOHOL ESTERS USING MIXED CATALYSTS. | |
| BRPI1005904A2 (en) | Process for the Production of Alkyl Esters from Vegetable or Animal Oil and a Fixed-Layer Hot-Purified Aliphatic Mono-Alcohol | |
| KR101068112B1 (en) | Method for preparing tungsten oxide alumina catalyst, tungsten oxide alumina catalyst and method for removing free fatty acid from waste cooking oil containing free fatty acid using the catalyst | |
| CN101704728B (en) | Method for preparing bisphenol compound antioxidant product by using organic acid catalyst | |
| WO2015069129A1 (en) | Process and catalyst for obtaining fatty acid methyl esters | |
| KR100782126B1 (en) | Tungsten oxide zirconia catalyst for removing free fatty acid in used soybean oil and application thereof | |
| KR100956414B1 (en) | Manufacture of Biodiesel from Fleshing scrap | |
| Cabrera-Munguia et al. | Tailoring the Suitable Solid Catalyst for Biodiesel Production Using Second-Generation Feedstocks | |
| KR101402473B1 (en) | Purification process for high purity methylester | |
| Abbasov et al. | Amine-containing complexes as catalysts for receiving alkyl esters of triglycerides, vegetable oils and their fatty acids | |
| Marciniuk et al. | Bioenergy II: Acid diphosphates as catalysts for the production of methyl and ethyl esters from vegetable oils |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20130326 Year of fee payment: 8 |
|
| FPAY | Annual fee payment |
Payment date: 20140310 Year of fee payment: 9 |
|
| FPAY | Annual fee payment |
Payment date: 20160311 Year of fee payment: 11 |
|
| FPAY | Annual fee payment |
Payment date: 20170102 Year of fee payment: 12 |
|
| FPAY | Annual fee payment |
Payment date: 20180209 Year of fee payment: 13 |
|
| FPAY | Annual fee payment |
Payment date: 20181211 Year of fee payment: 14 |
|
| FPAY | Annual fee payment |
Payment date: 20191210 Year of fee payment: 15 |