KR100996965B1 - Catalyst for producing bio-diesel and method for preparing bio-diesel using the same - Google Patents

Catalyst for producing bio-diesel and method for preparing bio-diesel using the same Download PDF

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KR100996965B1
KR100996965B1 KR1020090006175A KR20090006175A KR100996965B1 KR 100996965 B1 KR100996965 B1 KR 100996965B1 KR 1020090006175 A KR1020090006175 A KR 1020090006175A KR 20090006175 A KR20090006175 A KR 20090006175A KR 100996965 B1 KR100996965 B1 KR 100996965B1
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신중두
조재우
박상원
소규호
장용선
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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Abstract

본 발명은 바이오디젤 제조용 고체 촉매제 및 이를 이용한 바이오디젤의 제조방법에 관한 것이다. The present invention relates to a solid catalyst for biodiesel production and a method for producing biodiesel using the same.

본 발명의 고체 촉매제는 Ca(OH)2과 KOH를 혼합하고 소성하여 이루어지는 것을 특징으로 하고, 본 발명의 고체 촉매제 제조방법은 Ca(OH)2 용액과 KOH 용액을 혼합하여 70 내지 120℃에서 건조시키고, 300 내지 700℃에서 소성시켜 제조되는 것을 특징으로 한다. 본 발명의 바이오디젤 제조방법은, 식물성 유지와 알코올을 혼합하여 바이오디젤을 제조하는 방법에 있어서, 상기한 고체 촉매제를 첨가하여 반응시키는 것을 특징으로 한다. The solid catalyst of the present invention is characterized by mixing and calcining Ca (OH) 2 and KOH, the solid catalyst preparation method of the present invention is dried at 70 to 120 ℃ by mixing Ca (OH) 2 solution and KOH solution And it is characterized in that the produced by firing at 300 to 700 ℃. The biodiesel production method of the present invention is a method for producing biodiesel by mixing vegetable oils and alcohols, wherein the solid catalyst is added and reacted.

본 발명의 고체 촉매제를 이용하여 바이오디젤을 제조하면, 바이오디젤 전환효율을 높여 다량의 바이오디젤 생산이 가능하고, 잉여 촉매제의 정제과정이 생략됨으로써 공정이 단순화되고 오폐수 발생을 근절시킬 수 있다. When the biodiesel is manufactured using the solid catalyst of the present invention, biodiesel conversion efficiency can be increased to produce a large amount of biodiesel, and the purification process of the excess catalyst is omitted, thereby simplifying the process and eradicating wastewater generation.

바이오디젤, 고체 촉매제, 수산화칼슘, 수산화칼륨 Biodiesel, Solid Catalysts, Calcium Hydroxide, Potassium Hydroxide

Description

바이오디젤 제조용 고체 촉매제 및 이를 이용한 바이오디젤의 제조방법{CATALYST FOR PRODUCING BIO-DIESEL AND METHOD FOR PREPARING BIO-DIESEL USING THE SAME}CATALYST FOR PRODUCING BIO-DIESEL AND METHOD FOR PREPARING BIO-DIESEL USING THE SAME}

본 발명은 바이오디젤 제조용 고체 촉매제 및 이를 이용한 바이오디젤의 제조방법에 관한 것으로, 보다 상세하게는 식물성 유지로부터 바이오디젤을 합성시 바이오디젤 합성 효율을 높일 수 있는 고체 촉매제와 이 고체 촉매제를 이용하여 바이오디젤을 다량 제조할 수 있는 방법에 관한 것이다. The present invention relates to a solid catalyst for producing biodiesel and a method for producing biodiesel using the same. More specifically, the present invention relates to a solid catalyst capable of increasing biodiesel synthesis efficiency when synthesizing biodiesel from vegetable fats and oils using the solid catalyst. A method for producing a large amount of diesel.

화석연료 사용에 따른 지구온난화 및 환경오염 문제가 심각하게 대두되고 있는 오늘날 바이오디젤에 대한 연구가 다각도로 이루어지고 있다. Global warming and environmental pollution caused by the use of fossil fuels are becoming serious, and research on biodiesel is being conducted at various angles.

바이오디젤(bio-diesel)은 바이오에탄올과 함께 가장 널리 사용되는 바이오연료(bio-fuel)로, 콩기름·유채기름·폐식물기름·해조유(海藻油) 등의 식물성 기름을 원료로 하여 만든 식물성 연료를 통틀어 일컫는다. Bio-diesel is the most widely used bio-fuel with bioethanol. It is a vegetable made from vegetable oils such as soybean oil, rapeseed oil, waste vegetable oil and seaweed oil. Collectively referred to as fuel.

기존의 바이오디젤 제조방법으로는, 식물성 유지에 메탄올을 혼합하고 여기에 촉매제로서 KOH와 NaOH를 넣어 제조하는 방법이 있으나 이는 바이오디젤(지식경제부 바이오디젤 품질 고시기준 항목 중 하나인 메틸에스테르 함량 기준 96.5%) 전 환율이 75% 수준에 지나지 않았으며, 또한 KOH 및 NaOH가 메탄올에 녹을 때, 인체 유해물질인 메톡사이드(methoxide)로 전환됨에 따라 바이오디젤을 정제하는 과정에서 이를 제거하기 위하여 별도의 과정이 수반되어야 했다. Existing biodiesel manufacturing method is a method of mixing methanol in vegetable oil and adding KOH and NaOH as catalysts, but this is biodiesel (based on methyl ester content, which is one of the criteria for quality assessment of biodiesel, Ministry of Knowledge Economy). %) The total exchange rate was only 75%, and when KOH and NaOH were dissolved in methanol, it was converted into methoxide, which is a human harmful substance. This had to be accompanied.

또한 KOH와 NaOH를 사용할 경우에는, 합성된 바이오디젤에 촉매제가 남아 있어 물로 세척하고 이를 제거하는 별도의 과정이 필요하였다. 즉 세척과정에서 첨가된 수분은 열처리를 통하여 제거하여야 함으로써 공정이 복잡하고 많은 비용이 소요되는 문제점이 있었다. In addition, when KOH and NaOH were used, a catalyst remained in the synthesized biodiesel, which required a separate process of washing with water and removing it. That is, the water added in the washing process has to be removed through heat treatment, which causes a complicated process and a high cost.

이에, 본 발명의 발명자들은 심혈을 기울여 연구한 결과, 에스테르의 전환 효율이 높은 고체 촉매제를 발명하고 이를 이용하여 바이오디젤을 제조함으로써 잉여 촉매제의 정제과정이 없이 간단한 공정으로 바이오디젤을 제조하는 방법을 개발하여 본 발명에 이르렀다. Therefore, the inventors of the present invention have studied carefully, and as a result, invented a solid catalyst having a high conversion efficiency of ester and preparing biodiesel using the same, thereby preparing a biodiesel in a simple process without purification of the excess catalyst. The present invention has been developed.

본 발명의 목적은 바이오디젤 합성 효율이 우수하고 재사용이 가능한 고체 촉매제를 제공하는 것이다. An object of the present invention is to provide a solid catalyst which is excellent in biodiesel synthesis efficiency and reusable.

본 발명의 다른 목적은 바이오디젤 합성 효율이 우수하고 재사용이 가능한 고체 촉매제 제조방법을 제공하는 것이다. Another object of the present invention is to provide a method for preparing a solid catalyst which is excellent in biodiesel synthesis efficiency and reusable.

본 발명의 또 다른 목적은 간단한 공정으로 바이오디젤을 다량 생산할 수 있는 바이오디젤 제조방법을 제공하는 것이다. Still another object of the present invention is to provide a biodiesel manufacturing method capable of producing a large amount of biodiesel in a simple process.

본 발명의 바이오디젤 제조용 고체 촉매제는, Ca(OH)2과 KOH를 혼합하고 소성하여 이루어지는 것을 특징으로 한다. The solid catalyst for biodiesel production of the present invention is characterized by mixing and calcining Ca (OH) 2 and KOH.

본 발명의 바이오디젤 제조용 고체 촉매제 제조방법은, Ca(OH)2 용액과 KOH 용액을 혼합하여 70 내지 120℃에서 건조시키고, 300 내지 700℃에서 소성시켜 제조되는 것을 특징으로 한다. The solid catalyst preparation method for producing biodiesel according to the present invention is characterized in that the Ca (OH) 2 solution and the KOH solution are mixed, dried at 70 to 120 ° C., and calcined at 300 to 700 ° C.

본 발명의 바이오디젤 제조방법은, Biodiesel manufacturing method of the present invention,

식물성 유지와 알코올을 혼합하여 바이오디젤을 제조하는 방법에 있어서, In the method for producing biodiesel by mixing vegetable oil and alcohol,

상기에서 제조된 바이오디젤 제조용 고체 촉매제를 첨가하여 반응시키는 것을 특징으로 한다. It is characterized by reacting by adding the solid catalyst for biodiesel production prepared above.

본 발명의 고체 촉매제를 이용하여 바이오디젤을 제조하면, 바이오디젤 전환효율을 높여 다량의 바이오디젤 생산이 가능하고, 잉여 촉매제의 정제과정이 생략됨으로써 공정이 단순화되고 오폐수 발생을 근절시킬 수 있다. When the biodiesel is manufactured using the solid catalyst of the present invention, biodiesel conversion efficiency can be increased to produce a large amount of biodiesel, and the purification process of the excess catalyst is omitted, thereby simplifying the process and eradicating wastewater generation.

또한 본 발명의 고체 촉매제는 회수가 용이하고 재사용이 가능하여 경제적이다.In addition, the solid catalyst of the present invention is economical because it can be easily recovered and reused.

본 발명의 바이오디젤 제조용 고체 촉매제는, Ca(OH)2과 KOH를 혼합하고 소성하여 이루어지는 것을 특징으로 한다. 본 발명의 바이오디젤 제조용 고체 촉매제는 반응물질에 녹지 않고 반응만 촉진시킴으로써 반응 완료후 회수하여 재사용이 가능하다. The solid catalyst for biodiesel production of the present invention is characterized by mixing and calcining Ca (OH) 2 and KOH. The solid catalyst for producing biodiesel of the present invention is not dissolved in the reactants, thereby promoting the reaction and recovering the reaction after completion of the reaction.

본 발명의 바이오디젤 제조용 고체 촉매제 제조방법은, Ca(OH)2 용액과 KOH 용액을 혼합하여 70 내지 120℃에서 건조시키고, 300 내지 700℃에서 소성시켜 제조되는 것을 특징으로 한다. The solid catalyst preparation method for producing biodiesel according to the present invention is characterized in that the Ca (OH) 2 solution and the KOH solution are mixed, dried at 70 to 120 ° C., and calcined at 300 to 700 ° C.

본 발명의 바이오디젤 제조용 고체 촉매제 제조방법에서는 Ca(OH)2 용액과 KOH 용액을 쓰는 것이 바람직하다. 이는 Ca(OH)2과 KOH를 균일하게 혼합하기 위함이다. Ca(OH)2 용액과 KOH 용액을 70 내지 120℃에서 건조시키는 것은 소성시 에너지 효율을 높이기 위함이다. 바람직한 건조 온도는 100 내지 120℃이다. In the method for producing a solid catalyst for producing biodiesel of the present invention, it is preferable to use Ca (OH) 2 solution and KOH solution. This is to uniformly mix Ca (OH) 2 and KOH. Drying the Ca (OH) 2 solution and the KOH solution at 70 to 120 ° C. is intended to increase energy efficiency during firing. Preferable drying temperature is 100-120 degreeC.

본 발명의 바이오디젤 제조용 고체 촉매제 제조방법에서 건조된 Ca(OH)2-KOH 혼합물은 300 내지 700℃에서 소성시킨다. Ca(OH)2-KOH 혼합물을 300℃ 미만에서 소성시키면 최종 생산된 촉매제의 활성도가 떨어지는 문제점이 있다. 즉 바이오디젤 제조시 에스테르 생성 효율이 떨어지고 반응시간이 지연된다. 또한 Ca(OH)2-KOH 혼합물을 700℃ 초과 온도에서 소성시키면 추가되는 효과없이 경제적이지 못한 문제점이 있다. In the method for preparing a solid catalyst for preparing biodiesel of the present invention, the dried Ca (OH) 2 -KOH mixture is calcined at 300 to 700 ° C. When the Ca (OH) 2 -KOH mixture is calcined at less than 300 ° C., there is a problem in that the activity of the final produced catalyst is lowered. That is, the production efficiency of esters during biodiesel production is reduced and the reaction time is delayed. In addition, when the Ca (OH) 2 -KOH mixture is calcined at a temperature above 700 ℃ there is a problem that is not economical without the added effect.

본 발명의 바이오디젤 제조용 고체 촉매제 제조방법에서 바람직하게 사용되는 Ca(OH)2 용액의 농도는 0.1M 내지 10M이고, KOH 용액의 농도는 0.1M 내지 10M이다. Ca(OH)2 용액과 KOH 용액의 보다 바람직한 농도는 0.5M 내지 5M이다.The concentration of Ca (OH) 2 solution, which is preferably used in the solid catalyst preparation method for producing biodiesel of the present invention, is 0.1M to 10M, and the concentration of KOH solution is 0.1M to 10M. The more preferable concentration of Ca (OH) 2 solution and KOH solution is 0.5M to 5M.

본 발명의 바이오디젤 제조용 고체 촉매제 제조방법에서 Ca(OH)2 용액과 KOH 용액의 혼합비는 부피비 기준으로 1:0.05 내지 1:0.5인 것이 바람직하다. In the method for preparing a solid catalyst for preparing biodiesel of the present invention, the mixing ratio of Ca (OH) 2 solution and KOH solution is preferably 1: 0.05 to 1: 0.5 based on volume ratio.

본 발명의 바이오디젤 제조용 고체 촉매제 제조방법에서 Ca(OH)2 용액과 KOH 용액을 혼합하여 건조시 바람직한 건조시간은 3 내지 30시간이고, 건조후 바람직한 소성시간은 1 내지 5시간이다. 보다 바람직한 건조시간은 10 내지 24시간이고, 건조후 보다 바람직한 소성시간은 2 내지 4시간이다. In the method of preparing a solid catalyst for preparing biodiesel according to the present invention, a preferable drying time for drying by mixing Ca (OH) 2 solution and KOH solution is 3 to 30 hours, and a preferable firing time after drying is 1 to 5 hours. More preferable drying time is 10 to 24 hours, and more preferable firing time after drying is 2 to 4 hours.

한편, 본 발명의 바이오디젤 제조용 고체 촉매제 제조방법에서 Ca(OH)2 용액을 제조시 사용되는 Ca(OH)2 는 70 내지 120℃에서 3시간 내지 30시간 동안 건조시킨 Ca(OH)2를 사용하는 것이 바람직하다. 이는 Ca(OH)2 에 함유된 수분을 최대한 제거하기 위함이다. 보다 바람직하게는 Ca(OH)2를 100 내지 120℃에서 10시간 내지 24시간 동안 건조시킨다.On the other hand, use of Ca (OH) 2, Ca (OH) 2 is 70 Ca to that at 120 ℃ dried for 3 hours to 30 hours (OH) used in the manufacture of a solution 2 in biodiesel for preparing the solid catalyst production process of the present invention It is desirable to. This is to remove the moisture contained in Ca (OH) 2 as much as possible. More preferably Ca (OH) 2 is dried at 100 to 120 ° C. for 10 to 24 hours.

이어, 본 발명의 고체 촉매제를 이용하여 바이오디젤을 제조하는 방법을 설명한다. Next, a method for producing biodiesel using the solid catalyst of the present invention will be described.

본 발명의 바이오디젤 제조방법은, 식물성 유지와 알코올을 혼합하여 바이오디젤을 제조하는 방법에 있어서, 상기에서 제조된 바이오디젤 제조용 고체 촉매제를 첨가하여 반응시키는 것을 특징으로 한다. The biodiesel production method of the present invention is a method for producing biodiesel by mixing vegetable oil and alcohol, characterized in that the reaction by adding the solid catalyst for biodiesel production prepared above.

본 발명의 바이오디젤 제조방법에서 식물성 유지는 대두유, 유채유, 옥수수유, 평지유, 해바라기유, 피마자유, 팜유, 아마인유, 양귀비유, 호두유, 땅콩유, 면실유, 미강유, 동백유, 올리브유, 및 이들의 반복 사용으로 산가가 높아진 폐유로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 한다. Vegetable oil in the biodiesel manufacturing method of the present invention is soybean oil, rapeseed oil, corn oil, rapeseed oil, sunflower oil, castor oil, palm oil, linseed oil, poppy oil, walnut oil, peanut oil, cottonseed oil, rice bran oil, camellia oil, olive oil, and It is characterized in that at least one selected from the group consisting of waste oil having a high acid value by repeated use of these.

본 발명의 바이오디젤 제조방법에서 알코올은 메탄올, 에탄올, 프로판올 및 부탄올로 이루어진 군에서 적어도 하나 이상 선택되는 것을 특징으로 한다. Alcohol in the biodiesel manufacturing method of the present invention is characterized in that at least one selected from the group consisting of methanol, ethanol, propanol and butanol.

본 발명의 바이오디젤 제조방법에서 유지와 알코올의 몰비는 1:5 내지 1:20인 것을 특징으로 한다. 유지와 알코올의 몰비가 1:5 미만일 경우에는 바이오디젤 전환율이 떨어지는 문제점이 있고, 유지와 알코올의 몰비가 1:20을 초과할 경우에는 경제적이지 못한 문제점이 있다. In the biodiesel manufacturing method of the present invention, the molar ratio of fats and oils is 1: 5 to 1:20. When the molar ratio of fats and oils is less than 1: 5, there is a problem that the biodiesel conversion falls, and when the molar ratios of fats and oils exceeds 1:20, there is a problem that is not economical.

본 발명의 바이오디젤 제조방법에서 고체 촉매제는 유지 중량에 대하여 1 내지 12% 첨가되는 것이 바람직하다. 고체 촉매제의 첨가량이 1% 미만일 경우에는 바이오디젤 전환율이 떨어지는 문제점이 있고, 고체 촉매제의 첨가량이 12%를 초과할 경우에는 효과의 증진없이 경제적이지 못한 문제점이 있다.In the biodiesel manufacturing method of the present invention, the solid catalyst is preferably added 1 to 12% based on the holding weight. When the amount of the solid catalyst is less than 1%, there is a problem in that the biodiesel conversion is lowered. When the amount of the solid catalyst is more than 12%, there is a problem in that it is not economical without enhancement of the effect.

본 발명의 바이오디젤 제조방법에서 고체 촉매제의 입도가 20㎛ 미만인 것이 바람직하다. In the biodiesel production method of the present invention, the particle size of the solid catalyst is preferably less than 20 μm.

본 발명의 바이오디젤 제조방법에서 고체 촉매하에서 유지와 알코올의 반응은 초음파(ultra sonic energy)로 반응시키거나 기계적 교반(mechanical stirring)으로 반응시키는 것이 바람직하다. In the biodiesel production method of the present invention, the reaction between the fat and the alcohol under a solid catalyst is preferably performed by ultrasonic (ultra sonic energy) or by mechanical stirring.

본 발명의 바이오디젤 제조방법에서 반응은 50 내지 70℃에서 30분 내지 3시간 동안 반응시키는 것을 특징으로 한다. In the biodiesel manufacturing method of the present invention, the reaction is characterized in that the reaction for 30 minutes to 3 hours at 50 to 70 ℃.

특히, 본 발명의 바이오디젤 제조방법에서는 고체 촉매제의 크기 및 반응 방법에 따라 바이오디젤 제조 효율에 차이가 있다. In particular, in the biodiesel manufacturing method of the present invention, there is a difference in biodiesel manufacturing efficiency according to the size and reaction method of the solid catalyst.

본 발명의 바이오디젤 제조방법에서 보다 바람직한 반응 조건은, 2.5㎛ 미만의 고체 촉매제를 사용할 경우, 고체 촉매제의 첨가량을 유지 중량에 대하여 3 내지 5%로 하고 초음파로 반응시키는 것이다. 이 조건일때 제조된 바이오디젤에 함유 된 에스테르의 함량이 높고, 바이오디젤의 생산량이 높다.More preferable reaction conditions in the biodiesel production method of the present invention, when using a solid catalyst of less than 2.5㎛, the addition amount of the solid catalyst is 3 to 5% by the holding weight to react by ultrasonic waves. Under these conditions, the amount of ester contained in the produced biodiesel is high, and the biodiesel production is high.

본 발명의 바이오디젤 제조방법에서 보다 바람직한 반응 조건은, 5.0 내지 10.0㎛의 고체 촉매제를 사용할 경우, 고체 촉매제의 첨가량을 유지 중량에 대하여 7 내지 10%로 하고 기계적 교반으로 반응시키는 것이다. 이 조건일때 제조된 바이오디젤에 함유된 에스테르의 함량이 높고, 바이오디젤의 생산량이 높다. More preferred reaction conditions in the biodiesel production method of the present invention, when using a solid catalyst of 5.0 to 10.0㎛, the addition amount of the solid catalyst is 7 to 10% by the holding weight and reacted by mechanical stirring. Under these conditions, the amount of ester contained in the produced biodiesel is high, and the biodiesel production is high.

이하, 하기 실시예 및 비교예를 통하여 본 발명의 고체 촉매제 및 바이오디젤 제조방법을 보다 구체적으로 설명한다. Hereinafter, the solid catalyst and the biodiesel manufacturing method of the present invention will be described in more detail with reference to the following examples and comparative examples.

<실시예 1> 고체 촉매제 제조Example 1 Preparation of Solid Catalyst

1M Ca(OH)2 용액 900㎖와 1M KOH 용액 100㎖를 혼합한 후 110℃에서 24시간 동안 건조하고 500℃에서 3시간 동안 소성하여 얻어진 소성물을 분쇄하여 고체 촉매제를 제조하였다. 메시를 이용하여 2.5㎛ 미만의 고체 촉매제(A), 2.5 내지 5.0의 고체 촉매제(B), 5.0 내지 10.0㎛의 고체 촉매제(C), 10.0 내지 20.0㎛의 고체 촉매제(D)로 분류하였다. 900 ml of 1 M Ca (OH) 2 solution and 100 ml of 1 M KOH solution were mixed, dried at 110 ° C. for 24 hours, and calcined at 500 ° C. for 3 hours to prepare a solid catalyst. The mesh was classified into a solid catalyst (A) of less than 2.5 μm, a solid catalyst (B) of 2.5 to 5.0, a solid catalyst (C) of 5.0 to 10.0 μm, and a solid catalyst (D) of 10.0 to 20.0 μm.

<실시예 2> 바이오디젤 제조Example 2 Biodiesel Preparation

식용유 200g과 메탄올 100g을 혼합하고 상기 실시예 1에서 제조된 고체 촉매제(A) 8g을 가하여 60℃에서 초음파발생기(42kHz)에서 90분간 반응시켰다. 원심분 리를 행하여 고체 촉매제를 분리하고, 정치하여 층분리를 통하여 바이오디젤(상층)과 글리세린(하층)을 분리하였다. 200 g of cooking oil and 100 g of methanol were mixed, and 8 g of the solid catalyst (A) prepared in Example 1 was added thereto, followed by reaction at 60 ° C. for 90 minutes in an ultrasonic generator (42 kHz). The solid catalyst was separated by centrifugation, left to stand, and biodiesel (upper layer) and glycerin (lower layer) were separated through layer separation.

<실시예 3> 바이오디젤 제조Example 3 Biodiesel Preparation

식용유 200g과 메탄올 100g을 혼합하고 상기 실시예 1에서 제조된 고체 촉매제(B) 16g을 가하여 60℃에서 90분간 초음파발생기(42kHz)에서 반응시켰다. 원심분리를 행하여 고체 촉매제를 분리하고, 정치하여 층분리를 통하여 바이오디젤(상층)과 글리세린(하층)을 분리하였다. 200 g of cooking oil and 100 g of methanol were mixed, and 16 g of the solid catalyst (B) prepared in Example 1 was added thereto, followed by reaction at 60 ° C. for 90 minutes in an ultrasonic generator (42 kHz). The solid catalyst was separated by centrifugation, left to stand, and biodiesel (upper layer) and glycerin (lower layer) were separated through layer separation.

<실시예 4> 바이오디젤 제조Example 4 Biodiesel Preparation

식용유 200g과 메탄올 100g을 혼합하고 상기 실시예 1에서 제조된 고체 촉매제(C) 16g을 가하여 60℃에서 120분간 회전교반하여 반응시켰다. 원심분리를 행하여 고체 촉매제를 분리하고, 정치하여 층분리를 통하여 바이오디젤(상층)과 글리세린(하층)을 분리하였다. 200 g of cooking oil and 100 g of methanol were mixed, and 16 g of the solid catalyst (C) prepared in Example 1 was added thereto, followed by rotation stirring at 60 ° C. for 120 minutes. The solid catalyst was separated by centrifugation, left to stand, and biodiesel (upper layer) and glycerin (lower layer) were separated through layer separation.

<실시예 5> 바이오디젤 제조Example 5 Biodiesel Preparation

식용유 200g과 메탄올 100g을 혼합하고 상기 실시예 1에서 제조된 고체 촉매제(D) 10g을 가하여 70℃에서 100분간 회전교반하여 반응시켰다. 원심분리를 행하여 고체 촉매제를 분리하고, 정치하여 층분리를 통하여 바이오디젤(상층)과 글리세린(하층)을 분리하였다.200 g of cooking oil and 100 g of methanol were mixed, and 10 g of the solid catalyst (D) prepared in Example 1 was added thereto, followed by reacting by rotating stirring at 70 ° C. for 100 minutes. The solid catalyst was separated by centrifugation, left to stand, and biodiesel (upper layer) and glycerin (lower layer) were separated through layer separation.

<실시예 6> <Example 6>

실시예 2의 과정을 행하고, 실시예 2의 과정 중에서 분리된 고체 촉매제를 2회~7회 사용하여 실시예 2를 반복하여 바이오디젤을 제조하였다. 고체 촉매제의 사 용 횟수에 따른 바이오디젤 내 메틸에스테르 함량 변화를 측정하고 도 1에 도시하였다.Example 2 was repeated, and Example 2 was repeated using the solid catalyst separated in the procedure of Example 2 twice to prepare biodiesel. The change in the methyl ester content in the biodiesel according to the number of times of use of the solid catalyst was measured and shown in FIG.

<실시예 7><Example 7>

실시예 4의 과정을 행하고, 실시예 4의 과정 중에서 분리된 고체 촉매제를 2회~7회 사용하여 실시예 4를 반복하여 바이오디젤을 제조하였다. 고체 촉매제의 사용 횟수에 따른 바이오디젤 내 메틸에스테르 함량 변화를 측정하고 도 2에 도시하였다.Example 4 was repeated, and Example 4 was repeated using the solid catalyst separated in the procedure of Example 4 twice to prepare biodiesel. The change in the methyl ester content in the biodiesel according to the number of times of use of the solid catalyst was measured and shown in FIG. 2.

<비교예>Comparative Example

식용유 60g과 메탄올 10g을 혼합하고 KOH 3g 및 NaOH 6g을 가하고 60℃에서 1시간 동안 교반하여 반응시켰다. 물을 가하여 촉매제를 세척, 제거하였다. 세척된 반응물을 정치하여 층분리를 통하여 바이오디젤(상층)과 글리세린(하층)을 분리하였다.60 g of cooking oil and 10 g of methanol were mixed, and 3 g of KOH and 6 g of NaOH were added thereto, followed by stirring at 60 ° C. for 1 hour. Water was added to wash and remove the catalyst. The washed reaction was allowed to stand and the biodiesel (upper layer) and glycerin (lower layer) were separated by layer separation.

실시예 2~5 및 비교예에서 제조된 바이오디젤의 메틸에스테르 함량(%)과 바이오디젤 전환율(%)을 측정하여 표 1에 나타내었다.The methyl ester content (%) and biodiesel conversion (%) of the biodiesel prepared in Examples 2 to 5 and Comparative Examples were measured and shown in Table 1.

메틸에스테르 함량(%)Methyl Ester Content (%) 바이오디젤 전환율(%)Biodiesel Conversion Rate (%) 실시예 2 Example 2 98.798.7 93.693.6 실시예 3 Example 3 96.696.6 90.290.2 실시예 4Example 4 97.397.3 96.396.3 실시예 5 Example 5 96.596.5 93.293.2 비교예 Comparative example 96.596.5 74.574.5

표 1에서 알 수 있는 바와 같이, 실시예 2~5가 비교예에 비하여 바이오디젤 전환율이 높음을 알 수 있었다. As can be seen from Table 1, Examples 2 to 5 was found to have a higher biodiesel conversion compared to the Comparative Example.

도 1, 2에 도시된 바와 같이, 본 발명의 고체 촉매제는 4회까지 사용하여도 제조된 바이오디젤의 에스테르 함량이 96.5%를 유지함을 알 수 있었다. 따라서 본 발명의 고체 촉매제는 사용후 수차례 재사용 가능함으로써 비용을 경감할 수 있다.As shown in Figures 1 and 2, the solid catalyst of the present invention was found to maintain 96.5% of the ester content of the prepared biodiesel even when used up to four times. Therefore, the solid catalyst of the present invention can be reusable several times after use, thereby reducing the cost.

이상에서 본 발명의 구체예가 제시되어 있지만 본 발명이 상기에 한정되는 것은 아니며 본 발명의 기술 사상 범위 내에서 다양하게 변형 가능하고 이러한 변형은 하기한 본 발명의 청구범위에 속한다 할 것이다. Specific embodiments of the present invention have been presented above, but the present invention is not limited to the above, and various modifications can be made within the technical spirit of the present invention, and such modifications will belong to the following claims.

도 1은 본 발명에 의한 고체 촉매제의 사용횟수에 따른 메틸에스테르 함량 변화를 나타낸 도이다(초음파 이용). 1 is a diagram showing the change in the methyl ester content according to the number of times of use of the solid catalyst according to the present invention (using ultrasonic waves).

도 2는 본 발명에 의한 고체 촉매제의 사용횟수에 따른 메틸에스테르 함량 변화를 나타낸 도이다(회전교반). Figure 2 is a diagram showing the change in the methyl ester content according to the number of times of use of the solid catalyst according to the present invention (rotary stirring).

Claims (16)

Ca(OH)2과 KOH를 혼합하고 소성하여 이루어지는 것을 특징으로 바이오디젤 제조용 고체 촉매제.A solid catalyst for biodiesel production, characterized by mixing and firing Ca (OH) 2 and KOH. Ca(OH)2 용액과 KOH 용액을 혼합하여 70 내지 120℃에서 건조시키고, 300 내지 700℃에서 소성시켜 제조되는 것을 특징으로 하는 바이오디젤 제조용 고체 촉매제 제조방법.Mixing Ca (OH) 2 solution and KOH solution, and dried at 70 to 120 ℃, it is prepared by firing at 300 to 700 ℃ characterized in that the manufacturing method of a solid catalyst for biodiesel production. 청구항 2에 있어서, The method according to claim 2, 상기 Ca(OH)2 용액의 농도는 0.1M 내지 10M이고, KOH 용액의 농도는 0.1M 내지 10M인 것을 특징으로 하는 바이오디젤 제조용 고체 촉매제 제조방법.The concentration of the Ca (OH) 2 solution is 0.1M to 10M, the concentration of the KOH solution is 0.1M to 10M, characterized in that the method for producing a solid catalyst for biodiesel production. 청구항 2에 있어서,The method according to claim 2, 상기 Ca(OH)2 용액과 KOH 용액의 혼합비는 부피비 기준으로 1:0.05 내지 1:0.5인 것을 특징으로 하는 바이오디젤 제조용 고체 촉매제 제조방법.The mixing ratio of the Ca (OH) 2 solution and the KOH solution is 1: 0.05 to 1: 0.5 based on the volume ratio of the biodiesel production method for producing a solid catalyst. 청구항 2에 있어서, The method according to claim 2, 상기 건조 시간은 3시간 내지 30시간이고, 소성시간은 1 내지 5시간인 것을 특징으로 하는 바이오디젤 제조용 고체 촉매제 제조방법. The drying time is 3 hours to 30 hours, the firing time is 1 to 5 hours, characterized in that the biocatalyst manufacturing method for producing a solid catalyst. 청구항 2에 있어서,The method according to claim 2, 상기 Ca(OH)2 용액은, 70 내지 120℃에서 3시간 내지 30시간 동안 건조시킨 Ca(OH)2를 사용하는 것을 특징으로 하는 바이오디젤 제조용 고체 촉매제 제조방법.The Ca (OH) 2 solution, the method of producing a solid catalyst for biodiesel, characterized in that using Ca (OH) 2 dried for 3 to 30 hours at 70 to 120 ℃. 식물성 유지와 알코올을 혼합하여 바이오디젤을 제조하는 방법에 있어서, In the method for producing biodiesel by mixing vegetable oil and alcohol, 청구항 1의 바이오디젤 제조용 고체 촉매제를 첨가하여 반응시키는 것을 특징으로 하는 바이오디젤 제조방법. A biodiesel manufacturing method comprising adding and reacting a solid catalyst for biodiesel production according to claim 1. 청구항 7에 있어서,The method of claim 7, 상기 식물성 유지는 대두유, 유채유, 옥수수유, 평지유, 해바라기유, 피마자유, 팜유, 아마인유, 양귀비유, 호두유, 땅콩유, 면실유, 미강유, 동백유, 올리브유, 및 이들의 반복 사용으로 산가가 높아진 폐유로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 바이오디젤의 제조방법.The vegetable fats and oils, soybean oil, rapeseed oil, corn oil, rapeseed oil, sunflower oil, castor oil, palm oil, linseed oil, poppy oil, walnut oil, peanut oil, cottonseed oil, rice bran oil, camellia oil, olive oil, and their acid value by repeated use thereof Method for producing biodiesel, characterized in that at least one selected from the group consisting of high waste oil. 청구항 7에 있어서,The method of claim 7, 상기 유지와 알코올의 몰비는 1:5 내지 1:20인 것을 특징으로 하는 바이오디젤 제조방법. The molar ratio of the oil and alcohol is 1: 5 to 1:20 biodiesel manufacturing method characterized in that. 청구항 7에 있어서,The method of claim 7, 상기 고체 촉매제는 유지 중량에 대하여 1 내지 12% 첨가되는 것을 특징으로 하는 바이오디젤 제조방법.The solid catalyst is a biodiesel manufacturing method, characterized in that added to 1 to 12% by weight based on fat. 청구항 7에 있어서,The method of claim 7, 상기 고체 촉매제의 입도가 20㎛ 미만인 것을 특징으로 하는 바이오디젤 제조방법. Biodiesel production method characterized in that the particle size of the solid catalyst is less than 20㎛. 청구항 7에 있어서,The method of claim 7, 초음파로 반응시키는 것을 특징으로 하는 바이오디젤 제조방법. Biodiesel manufacturing method characterized in that the reaction by ultrasonic. 청구항 7에 있어서,The method of claim 7, 기계적 교반하여 반응시키는 것을 특징으로 하는 바이오디젤 제조방법. Biodiesel production method characterized in that the reaction by mechanical stirring. 청구항 7에 있어서,The method of claim 7, 50 내지 70℃에서 30분 내지 3시간 동안 반응시키는 것을 특징으로 하는 바이오디젤 제조방법.Biodiesel manufacturing method characterized in that the reaction for 30 minutes to 3 hours at 50 to 70 ℃. 청구항 7에 있어서,The method of claim 7, 상기 고체 촉매제의 입도가 2.5㎛ 미만이고 상기 고체 촉매제의 첨가량은 유지 중량에 대하여 3 내지 5% 첨가되며, 초음파로 반응시키는 것을 특징으로 하는 바이오디젤 제조방법.The particle size of the solid catalyst is less than 2.5㎛ and the addition amount of the solid catalyst is 3 to 5% by weight based on the holding weight, biodiesel manufacturing method characterized in that the reaction by ultrasonic. 청구항 7에 있어서,The method of claim 7, 상기 고체 촉매제의 입도가 5.0 내지 10.0㎛이고 상기 고체 촉매제의 첨가량은 유지 중량에 대하여 7 내지 10% 첨가되며, 회전교반으로 반응시키는 것을 특징으로 하는 바이오디젤 제조방법.The particle size of the solid catalyst is 5.0 to 10.0㎛ and the amount of the solid catalyst is added 7 to 10% by weight based on the holding weight, biodiesel manufacturing method characterized in that the reaction by rotary stirring.
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