WO2019004513A1 - Pretreatment method for early activation of ceramic solid catalyst to be used in production of fatty acid methyl ester - Google Patents
Pretreatment method for early activation of ceramic solid catalyst to be used in production of fatty acid methyl ester Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/28—Molybdenum
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- B01J35/19—Catalysts containing parts with different compositions
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
Definitions
- the present invention relates to a pretreatment method for the early activation of ceramic solid catalysts used in the production of fatty acid methyl esters from fatty acid containing fats.
- a method of synthesizing a fatty acid methyl ester from a low-cost non-edible oil having a high fatty acid content has been actively studied and a mixture of a fatty acid and triglyceride is synthesized through a transesterification reaction (Scheme 1) and an esterification reaction (Scheme 2)
- Scheme 1 transesterification reaction
- Scheme 2 esterification reaction
- Such solid catalysts include ceramic solid catalysts composed of SnO, TiO 2 , MoO 3 and aluminum silicate.
- the activity of the catalyst gradually develops as shown in Table 1 below, and the high purity Fatty acid methyl esters are obtained.
- a method for activating a solid catalyst for the production of fatty acid methyl esters which comprises immersing a solid catalyst used for preparing a fatty acid methyl ester from a fatty acid-containing fat in a pretreatment liquid containing the fatty acid-containing fat.
- a process for preparing a fatty acid methyl ester comprising preparing a fatty acid methyl ester from a fatty acid-containing fat by a batch process using a solid catalyst activated by the method according to any one of the above 1 to 8.
- the vegetable oil is composed of soybean oil, rapeseed oil, sunflower oil, palm oil, corn oil, cottonseed oil, castor oil, jatropha oil, coconut oil, palm kernel oil, fish oil, ≪ / RTI > wherein at least one of the fatty acid methyl esters is selected from the group consisting of:
- a method of pre-treating a ceramic solid catalyst used for converting an isobutylene vegetable oil having a high fatty acid content into methanol and a fatty acid methyl ester, so that the activity of the solid catalyst can be expressed early in the production process and A solid acid catalyst activated by the above method was used to provide a process for obtaining fatty acid methyl esters of high purity from the first step of the vegetable oil having high fatty acid content by a batch process.
- the activity of the solid catalyst is expressed early, the activity of the conventional ceramic solid catalyst is gradually developed, thereby preventing the economic loss occurring in the actual production process.
- Figure 1 is a schematic representation of a reactor used to prepare fatty acid methyl esters using a solid catalyst.
- FIG. 2 is a schematic diagram of a method for pretreating a ceramic solid catalyst used to produce a fatty acid methyl ester from a high fatty acid content oil according to the present invention.
- the inventors of the present invention have found that when a ceramic solid catalyst used for preparing a fatty acid methyl ester from a fatty acid-containing fat is immersed in the fatty acid-containing oil and pretreated, the solid catalyst is activated early, Fatty acid methyl esters having a purity of 85% or higher can be obtained from the first reaction in a batch process in the case of preparing fatty acid methyl esters from a fatty acid-containing fat, thereby completing the present invention.
- the present invention relates to a method for activating a solid catalyst for the production of fatty acid methyl esters, comprising immersing a solid catalyst used in preparing a fatty acid methyl ester from a fatty acid-containing fat in a pretreatment liquid containing the fatty acid-containing fat.
- the pretreatment liquid has a hydrophilic substance content within 20% by volume, and the hydrophilic substance may be an alcohol having 1 to 6 carbon atoms, preferably methanol, ethanol, propanol, butanol, 2-ethylhexanol, And may be one or more selected from the group.
- the hydrophilic substance may be an alcohol having 1 to 6 carbon atoms, preferably methanol, ethanol, propanol, butanol, 2-ethylhexanol, And may be one or more selected from the group.
- the temperature of the pretreatment liquid is preferably maintained in the range of 20 to 100 ° C.
- the solid catalyst is a solid catalyst comprising a ceramic solid catalyst, preferably SnO, TiO2, MoO3 and aluminum silicate, which are used to prepare fatty acid methyl esters from fatty acid containing fats, more preferably SnO, TiO2 And a catalyst in which MoO3 is supported on aluminum silicate, most preferably 3.5 to 54.0 wt% of SnO, 0.5 to 1.5 wt% of TiO2, 0.5 to 1.5 wt% of MoO3, and 40 to 95 wt% of aluminum silicate.
- a ceramic solid catalyst preferably SnO, TiO2, MoO3 and aluminum silicate, which are used to prepare fatty acid methyl esters from fatty acid containing fats, more preferably SnO, TiO2
- a catalyst in which MoO3 is supported on aluminum silicate most preferably 3.5 to 54.0 wt% of SnO, 0.5 to 1.5 wt% of TiO2, 0.5 to 1.5 wt% of MoO3, and 40 to 95 wt%
- the present invention also relates to a process for preparing fatty acid methyl esters from fatty acid containing fats by a batch process using the activated solid catalysts.
- a process for preparing fatty acid methyl esters from fatty acid containing fats by a batch process using the activated solid catalysts it is possible to obtain a fatty acid methyl ester having a purity of 85% or more from the first reaction in a batch process by pretreating the solid catalyst with a fat used in the production of fatty acid methyl esters, preferably fatty acid-containing fat.
- the fatty acid-containing fat may have a fatty acid content in the range of 50 to 100%. Therefore, in the present invention, the fatty acid-containing fat has a high acid content of not less than 50% in fatty acid content, and may be a fat-only fat.
- the fatty acid may be oleic acid.
- the fatty acid-containing fat may be selected from the group consisting of non-edible animal and vegetable fats, preferably soybean oil, rape oil, sunflower oil, palm oil, corn oil, cottonseed oil, castor oil, jatropha oil, coconut oil, palm kernel oil, The lungs being discarded in the lungs.
- 200 g of a sample prepared by mixing SnO, TiO 2 and MoO 3 , which are catalytically active materials, in various compositions were mixed with 800 g of aluminum silicate as a carrier material, and then mixed with a small amount of an adhesive aid and a lubricant.
- the catalyst mixture was filled into a cylindrical mold having a diameter of 10 mm and a length of 15 mm and molded to a uniform size by applying pressure.
- the cylindrical catalyst was sintered at 1,000 ° C for 60 minutes to prepare a ceramic solid catalyst.
- Example 1 160 ml of a raw material having a composition of 80% of soybean oil and 20% of oleic acid and 80 ml of methanol were mixed and then 20 g of the ceramic solid catalyst prepared in Example 1 was attached to a stirrer and the mixture was stirred at 220 ⁇ in a high- The fatty acid methyl ester was produced by stirring at a speed of 200 rpm for 4 hours.
- Example 1 50 ml of soybean oil and 50 ml of oleic acid were charged in a beaker and heated to 60 ° C. After 20 g of the ceramic solid catalyst prepared in Example 1 was added thereto and stirred for 12 hours, the solid catalyst was taken out and left at room temperature for 2 hours A pretreated solid catalyst was prepared.
- the pretreated solid catalyst was used to conduct experiments for the production of fatty acid methyl esters under the same conditions as in Comparative Example 1, and the results are shown in Table 3 below.
- the pretreatment of the ceramic solid catalyst was carried out by adding 0 to 50% methanol as a hydrophilic substance to the pretreatment liquid obtained by mixing 50 ml of soybean oil and 50 ml of oleic acid, and then conducting the experiment of producing methyl ester under the same conditions as in Comparative Example 1 , Respectively.
- Composition of pretreatment liquid Fatty acid methyl ester purity 1st round Second round Three times Four times 5 times 5 times Soybean oil 50%, oleic acid 50%, methanol 0% 90.8% 92.2% 91.5% 91.5% 90.3% 45% of soybean oil, 45% of oleic acid, 10% of methanol, 88.3% 91.7% 91.1% 91.6% 90.7% Soybean oil 40%, oleic acid 40%, methanol 20% 82.9% 90.3% 92.1% 91.0% 91.5% 35% soybean oil, 35% oleic acid, 30% methanol, 86.8% 87.1% 88.2% 91.0% 91.2% 30% of soybean oil, 30% of oleic acid, 40% of methanol, 83.4% 82.6% 85.8% 89.7% 92.4% 25% soybean oil, 25% oleic acid, 50% methanol, 79.3% 83.6% 89.2% 92.5% 91.7%
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Abstract
Description
본 발명은 지방산 함유 유지로부터 지방산 메틸 에스테르를 생산하는 데에 사용되는 세라믹 고체 촉매의 조기 활성화를 위한 전처리 방법에 관한 것이다.The present invention relates to a pretreatment method for the early activation of ceramic solid catalysts used in the production of fatty acid methyl esters from fatty acid containing fats.
지방산 함량이 높은 저가의 비식용 유지로부터 지방산 메틸 에스테르를 합성하는 방법이 활발하게 연구되면서, 지방산과 트리글리세라이드의 혼합물을 에스테르 교환 반응 (반응식 1) 및 에스테르화 반응 (반응식 2)을 통해 지방산 메틸 에스테르로 동시에 전환하는 데에 사용되는 비균질 촉매에 관한 연구가 활발하게 진행되고 있다. A method of synthesizing a fatty acid methyl ester from a low-cost non-edible oil having a high fatty acid content has been actively studied and a mixture of a fatty acid and triglyceride is synthesized through a transesterification reaction (Scheme 1) and an esterification reaction (Scheme 2) The catalysts used for the simultaneous conversion into the non-homogeneous catalyst have been actively studied.
[반응식 1][Reaction Scheme 1]
트리글리세라이드 + 메탄올 ↔ 지방산 메틸 에스테르 + 글리세롤Triglyceride + methanol? Fatty acid methyl ester + glycerol
[반응식 2][Reaction Scheme 2]
지방산 + 메탄올 ↔ 지방산 메틸 에스테르 + 물Fatty Acid + Methanol ↔ Fatty Acid Methyl Ester + Water
이러한 고체 촉매가 실제 지방산 메틸 에스테르의 생산 공정에 적용되는 경우 지방산이 다량 포함된 저가의 유지를 원료로 사용할 수 있게 되어 경제적이며, 반응 후 촉매를 분리하고 폐기물을 세척해 내는 공정을 생략할 수 있게 되어 친환경적인 공정 구현이 가능해진다.When such a solid catalyst is applied to a production process of a fatty acid methyl ester, it is economical to use a low-cost fat containing a large amount of fatty acid as a raw material, and it is possible to omit the process of separating the catalyst after the reaction and washing the waste And it becomes possible to realize an environmentally friendly process.
이러한 고체 촉매의 예로는 SnO, TiO2, MoO3 및 규산알루미늄으로 구성된 세라믹 고체 촉매가 있다. 그러나 이러한 촉매를 사용하여 지방산 함량이 높은 팜 산화유를 메탄올과 반응시켜 지방산 메틸 에스테르로 전환하는 경우 하기 표 1에서 보는 것처럼 촉매의 활성이 점진적으로 발현되어 회분식 반응에서 3회차 이후가 되어야 높은 순도의 지방산 메틸 에스테르가 얻어진다. Examples of such solid catalysts include ceramic solid catalysts composed of SnO, TiO 2 , MoO 3 and aluminum silicate. However, when the catalyst is converted into fatty acid methyl esters by reacting the high-fatty acid palm oil with methanol, the activity of the catalyst gradually develops as shown in Table 1 below, and the high purity Fatty acid methyl esters are obtained.
그러나 지방산 메틸 에스테르를 상업적으로 행산하고자 할 때 상기의 예처럼 고체 촉매의 활성이 천천히 발현된다면, 품질이 낮은 초기 생산 제품은 폐기하거나 추가적인 에너지를 사용하여 다시 반응시켜야 하므로 경제적 손실이 발생한다. However, if the activity of the solid catalyst is slowly expressed as in the above-mentioned example when the fatty acid methyl ester is to be commercially produced, economical loss occurs because the initial production product having low quality must be discarded or re-reacted using additional energy.
그러므로 실제 생산 공정에서 고체 촉매의 활성이 조기에 발현되도록 활성화하는 것이 필요하다.Therefore, it is necessary to activate the solid catalyst so that the activity of the solid catalyst is expressed early in the actual production process.
본 발명의 목적은 지방산 함량이 높은 동식물성 유지를 메탄올과 반응시켜 지방산 메틸 에스테르로 전환하는 데에 사용되는 세라믹 고체 촉매의 활성이 조기에 발현되도록 하는 방법을 제공하는 것이다.It is an object of the present invention to provide a method for early expression of the activity of a ceramic solid catalyst used for converting an isobutylene vegetable oil having a high fatty acid content into methanol and a fatty acid methyl ester.
본 발명의 다른 한 가지 목적은 활성화된 고체 촉매를 사용하여 회분식 공정으로 지방산 함량이 높은 동식물성 유지로부터 1회차부터 고순도의 지방산 메틸 에스테르를 수득하는 방법을 제공하는 것이다.It is another object of the present invention to provide a process for obtaining fatty acid methyl esters of high purity from a first order to a high fatty acid content by using an activated solid catalyst in a batch process.
본 발명에서 상술한 기술적 과제를 해결하는 수단은 다음과 같다.Means for solving the above-mentioned technical problems in the present invention are as follows.
1. 지방산 함유 유지로부터 지방산 메틸 에스테르를 제조하는 데에 사용되는 고체 촉매를 상기 지방산 함유 유지를 함유하는 전처리액에 침지시키는 것을 포함하는, 지방산 메틸 에스테르 제조용 고체 촉매의 활성화 방법. 1. A method for activating a solid catalyst for the production of fatty acid methyl esters, which comprises immersing a solid catalyst used for preparing a fatty acid methyl ester from a fatty acid-containing fat in a pretreatment liquid containing the fatty acid-containing fat.
2. 전처리액은 친수성 물질 함량이 20 부피% 이내인 상기 1의 고체 촉매의 활성화 방법.2. The method of claim 1, wherein the pretreatment liquid has a hydrophilic material content within 20 vol%.
3. 친수성 물질은 탄소 수 1 내지 6개의 알코올인 상기 2의 고체 촉매의 활성화 방법.3. The method for activating the solid catalyst of 2 above, wherein the hydrophilic substance is an alcohol having 1 to 6 carbon atoms.
4. 알코올은 메탄올, 에탄올, 프로판올, 부탄올, 2-에틸헥산올 및 이들의 혼합물로 구성된 군에서 하나 이상 선택되는 것인 상기 1의 고체 촉매의 활성화 방법.4. The method for activating a solid catalyst according to the above 1, wherein the alcohol is at least one selected from the group consisting of methanol, ethanol, propanol, butanol, 2-ethylhexanol and mixtures thereof.
5. 침지 중에 전처리액의 온도를 20~100℃ 범위로 유지하는 것인 상기 1의 고체 촉매의 활성화 방법.5. The method for activating a solid catalyst according to the above 1, wherein the temperature of the pretreatment liquid is maintained in the range of 20 to 100 占 폚 during immersion.
6. 고체 촉매를 전처리액에 6~72 시간 동안 침지시키는 것인 상기 1의 고체 촉매의 활성화 방법.6. A method of activating the solid catalyst of 1 above, wherein the solid catalyst is immersed in the pretreatment solution for 6 to 72 hours.
7. 고체 촉매는 SnO, TiO2, MoO3 및 규산알루미늄을 포함하는 것인 상기 1의 고체 촉매의 활성화 방법.7. The method of activating the solid catalyst of 1 above, wherein the solid catalyst comprises SnO, TiO2, MoO3 and aluminum silicate.
8. 고체 촉매는 SnO 3.5~54.0중량%, TiO2 0.5~1.5 중량%, MoO3 0.5~1.5 중량% 및 규산알루미늄 40~95 중량%를 포함하는 것인 상기 7의 고체 촉매의 활성화 방법.8. The method for activating a solid catalyst according to 7 above, wherein the solid catalyst comprises 3.5 to 54.0% by weight of SnO, 0.5 to 1.5% by weight of TiO2, 0.5 to 1.5% by weight of MoO3 and 40 to 95% by weight of aluminum silicate.
9. 상기 1 내지 8 중 어느 하나에 따른 방법으로 활성화한 고체 촉매를 이용하여 회분식 공정으로 지방산 함유 유지로부터 지방산 메틸 에스테르를 제조하는 것을 포함하는, 지방산 메틸 에스테르의 제조 방법. 9. A process for preparing a fatty acid methyl ester, comprising preparing a fatty acid methyl ester from a fatty acid-containing fat by a batch process using a solid catalyst activated by the method according to any one of the above 1 to 8.
10. 지방산 함유 유지는 지방산 함량이 50 내지 100% 범위인 상기 9의 지방산 메틸 에스테르의 제조 방법. 10. The method for producing fatty acid methyl esters of 9 above, wherein the fatty acid-containing fat has a fatty acid content in the range of 50 to 100%.
11. 지방산은 올레산인 상기 10의 지방산 메틸 에스테르의 제조 방법. 11. The method for producing the fatty acid methyl ester of the above 10, wherein the fatty acid is oleic acid.
12. 유지는 비식용 동식물성 유지인 상기 9의 지방산 메틸 에스테르의 제조 방법. 12. The method for producing fatty acid methyl esters of the above 9, wherein the oil is a non-edible copper vegetable oil.
13. 동식물성 유지는 대두유, 유채유, 해바라기유, 팜유, 옥수수유, 면실유, 피마자유, 자트로파유, 코코넛유, 팜핵유, 어유, 우지, 돈지 및 이들의 사용 이후에 버려지는 폐유지로 구성된 군에서 하나 이상 선택되는 것인 상기 12의 지방산 메틸 에스테르의 제조 방법.13. The vegetable oil is composed of soybean oil, rapeseed oil, sunflower oil, palm oil, corn oil, cottonseed oil, castor oil, jatropha oil, coconut oil, palm kernel oil, fish oil, ≪ / RTI > wherein at least one of the fatty acid methyl esters is selected from the group consisting of:
본 발명에 따라 지방산 함량이 높은 동식물성 유지를 메탄올과 반응시켜 지방산 메틸 에스테르로 전환하는 데에 사용되는 세라믹 고체 촉매를 전처리하여 생산 공정에서 고체 촉매의 활성이 조기에 발현될 수 있도록 하는 방법, 및 상기 방법으로 활성화한 고체 촉매를 사용하여 회분식 공정으로 지방산 함량이 높은 동식물성 유지로부터 1회차부터 고순도의 지방산 메틸 에스테르를 수득하는 방법을 제공하였다. According to the present invention, there is provided a method of pre-treating a ceramic solid catalyst used for converting an isobutylene vegetable oil having a high fatty acid content into methanol and a fatty acid methyl ester, so that the activity of the solid catalyst can be expressed early in the production process, and A solid acid catalyst activated by the above method was used to provide a process for obtaining fatty acid methyl esters of high purity from the first step of the vegetable oil having high fatty acid content by a batch process.
이와 같이 본 발명에서는 고체 촉매의 활성이 조기에 발현되도록 함으로써, 기존의 세라믹 고체 촉매의 활성이 점진적으로 발현되는 것으로 인해 실제 생산 공정에 적용 시에 발생하는 경제적 손실을 방지할 수 있도록 하였다. As described above, in the present invention, since the activity of the solid catalyst is expressed early, the activity of the conventional ceramic solid catalyst is gradually developed, thereby preventing the economic loss occurring in the actual production process.
도 1은 고체 촉매를 사용하여 지방산 메틸 에스테르를 제조하는 데에 사용되는 반응기의 개략도이다.BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of a reactor used to prepare fatty acid methyl esters using a solid catalyst.
도 2는 본 발명에 따라 지방산 함량이 높은 유지로부터 지방산 메틸 에스테르를 생산하는 데에 사용되는 세라믹 고체 촉매를 전처리하는 방법의 개략도이다.2 is a schematic diagram of a method for pretreating a ceramic solid catalyst used to produce a fatty acid methyl ester from a high fatty acid content oil according to the present invention.
본 발명의 발명자들은 지방산 함유 유지로부터 지방산 메틸 에스테르를 제조하는 데에 사용되는 세라믹 고체 촉매를 상기 지방산 함유 유지에 침지시켜 전처리하는 경우 상기 고체 촉매가 조기에 활성화되고, 이와 같이 활성화된 촉매를 사용하여 지방산 함유 유지로부터 지방산 메틸 에스테르를 제조는 경우 회분식 공정에서 1회차 반응부터 순도 85% 이상의 지방산 메틸 에스테르를 수득할 수 있다는 것을 밝혀내어 본 발명을 완성하였다. The inventors of the present invention have found that when a ceramic solid catalyst used for preparing a fatty acid methyl ester from a fatty acid-containing fat is immersed in the fatty acid-containing oil and pretreated, the solid catalyst is activated early, Fatty acid methyl esters having a purity of 85% or higher can be obtained from the first reaction in a batch process in the case of preparing fatty acid methyl esters from a fatty acid-containing fat, thereby completing the present invention.
따라서 본 발명은 지방산 함유 유지로부터 지방산 메틸 에스테르를 제조하는 데에 사용되는 고체 촉매를 상기 지방산 함유 유지를 함유하는 전처리액에 침지시키는 것을 포함하는, 지방산 메틸 에스테르 제조용 고체 촉매의 활성화 방법에 관한 것이다. Accordingly, the present invention relates to a method for activating a solid catalyst for the production of fatty acid methyl esters, comprising immersing a solid catalyst used in preparing a fatty acid methyl ester from a fatty acid-containing fat in a pretreatment liquid containing the fatty acid-containing fat.
상기 전처리액은 친수성 물질 함량이 20 부피% 이내인 것이 바람직하며, 상기 친수성 물질은 탄소 수 1 내지 6개의 알코올, 바람직하게는 메탄올, 에탄올, 프로판올, 부탄올, 2-에틸헥산올 및 이들의 혼합물로 구성된 군에서 하나 이상 선택되는 것일 수 있다. Preferably, the pretreatment liquid has a hydrophilic substance content within 20% by volume, and the hydrophilic substance may be an alcohol having 1 to 6 carbon atoms, preferably methanol, ethanol, propanol, butanol, 2-ethylhexanol, And may be one or more selected from the group.
상기 침지 중에 전처리액의 온도는 20~100℃ 범위로 유지하는 것이 바람직하다. During the immersion, the temperature of the pretreatment liquid is preferably maintained in the range of 20 to 100 ° C.
고체 촉매를 전처리액에 6~72 시간 동안 침지시키는 것이 바람직하다. It is preferable to immerse the solid catalyst in the pretreatment liquid for 6 to 72 hours.
상기 고체 촉매는 지방산 함유 유지로부터 지방산 메틸 에스테르를 제조하는 데에 사용되는 세라믹 고체 촉매, 바람직하게는 SnO, TiO2, MoO3 및 규산알루미늄을 포함하는 고체 촉매, 더욱 바람직하게는 촉매 활성 성분인 SnO, TiO2 및 MoO3가 규산알루미늄에 담지된 촉매, 가장 바람직하게는 SnO 3.5~54.0중량%, TiO2 0.5~1.5 중량%, MoO3 0.5~1.5 중량% 및 규산알루미늄 40~95 중량%를 포함하는 것일 수 있다. The solid catalyst is a solid catalyst comprising a ceramic solid catalyst, preferably SnO, TiO2, MoO3 and aluminum silicate, which are used to prepare fatty acid methyl esters from fatty acid containing fats, more preferably SnO, TiO2 And a catalyst in which MoO3 is supported on aluminum silicate, most preferably 3.5 to 54.0 wt% of SnO, 0.5 to 1.5 wt% of TiO2, 0.5 to 1.5 wt% of MoO3, and 40 to 95 wt% of aluminum silicate.
또한 본 발명은 상술한 방법으로 활성화한 고체 촉매를 이용하여 회분식 공정으로 지방산 함유 유지로부터 지방산 메틸 에스테르를 제조하는 방법에 관한 것이다. 본 발명에서는 고체 촉매를 지방산 메틸 에스테르 제조에 사용되는 유지, 바람직하게는 지방산 함유 유지로 전처리하여 조기 활성화함으로써 회분식 공정에서 1회차 반응부터 순도 85% 이상의 지방산 메틸 에스테르를 수득하는 것이 가능하다. The present invention also relates to a process for preparing fatty acid methyl esters from fatty acid containing fats by a batch process using the activated solid catalysts. In the present invention, it is possible to obtain a fatty acid methyl ester having a purity of 85% or more from the first reaction in a batch process by pretreating the solid catalyst with a fat used in the production of fatty acid methyl esters, preferably fatty acid-containing fat.
상기 지방산 함유 유지는 지방산 함량이 50 내지 100% 범위인 것일 수 있다. 따라서 본 발명에 있어서 상기 지방산 함유 유지는 지방산 함량 50% 이상의 고산가 유지이며, 지방산으로만 이루어진 유지일 수도 있다. 상기 지방산은 올레산일 수 있다.The fatty acid-containing fat may have a fatty acid content in the range of 50 to 100%. Therefore, in the present invention, the fatty acid-containing fat has a high acid content of not less than 50% in fatty acid content, and may be a fat-only fat. The fatty acid may be oleic acid.
상기 지방산 함유 유지는 비식용 동식물성 유지, 바람직하게는 대두유, 유채유, 해바라기유, 팜유, 옥수수유, 면실유, 피마자유, 자트로파유, 코코넛유, 팜핵유, 어유, 우지, 돈지 및 이들의 사용 이후에 버려지는 폐유지로 구성된 군에서 하나 이상 선택되는 것일 수 있다.The fatty acid-containing fat may be selected from the group consisting of non-edible animal and vegetable fats, preferably soybean oil, rape oil, sunflower oil, palm oil, corn oil, cottonseed oil, castor oil, jatropha oil, coconut oil, palm kernel oil, The lungs being discarded in the lungs.
실시예Example
이하에서는 본 발명을 실시예를 통해 더욱 상세히 설명한다. 그러나 실시예는 본 발명의 예시에 불과할 뿐, 본 발명의 범위를 실시예의 범위로 한정하고자 하는 것은 아니다. Hereinafter, the present invention will be described in more detail by way of examples. However, the embodiments are only examples of the present invention, and the scope of the present invention is not limited to the embodiments.
제조예Manufacturing example 1: 세라믹 고체 촉매의 제조 1: Preparation of ceramic solid catalyst
촉매 활성물질인 SnO, TiO2 및 MoO3를 다양한 조성으로 혼합한 시료 200g을 담체 물질인 규산알루미늄 800g과 혼합한 후, 소량의 접착보조제, 윤활보조제와 균일하게 섞어주었다. 200 g of a sample prepared by mixing SnO, TiO 2 and MoO 3 , which are catalytically active materials, in various compositions were mixed with 800 g of aluminum silicate as a carrier material, and then mixed with a small amount of an adhesive aid and a lubricant.
직경 10 mm, 길이 15 mm의 원기둥 형태의 성형 틀에 촉매 혼합물을 채워 압력을 가해 균일한 크기로 성형한 후, 원기둥 형태로 제조된 촉매를 1,000℃에서 60분간 소결하여 세라믹 고체 촉매를 제조하였다.The catalyst mixture was filled into a cylindrical mold having a diameter of 10 mm and a length of 15 mm and molded to a uniform size by applying pressure. The cylindrical catalyst was sintered at 1,000 ° C for 60 minutes to prepare a ceramic solid catalyst.
비교예Comparative Example 1: 세라믹 고체 촉매를 이용한 지방산 1: fatty acids using ceramic solid catalyst 메틸methyl 에스테르 생산 Ester production
대두유 80%, 올레익산 20%의 조성을 갖는 원료 160ml와 메탄올 80ml를 혼합한 후 실시예 1에서 제조한 세라믹 고체 촉매 20g을 교반기에 부착하여 도1에 예시된 것과 같은 고압 반응기에서 220℃의 조건으로 4시간 동안 200rpm의 속도로 교반하면서 지방산 메틸 에스테르를 생산하였다. 160 ml of a raw material having a composition of 80% of soybean oil and 20% of oleic acid and 80 ml of methanol were mixed and then 20 g of the ceramic solid catalyst prepared in Example 1 was attached to a stirrer and the mixture was stirred at 220 캜 in a high- The fatty acid methyl ester was produced by stirring at a speed of 200 rpm for 4 hours.
반응이 종료된 후 촉매는 새로운 원료를 지방산 메틸 에스테르로 전환하기 위한 다음 회차의 회분식 반응에 재사용하고, 각 회차에서 생산된 지방산 메틸 에스테르의 순도를 측정하여, 그 결과를 하기 표 2에 나타내었다. After the reaction was completed, the catalyst was reused for the next batch of reactions to convert the new raw materials to fatty acid methyl esters, and the purity of the fatty acid methyl esters produced at each reaction was measured. The results are shown in Table 2 below.
표 2에서 보는 것과 같이, 3회차 반응까지는 촉매가 완전히 활성화되지 않았음을 확인할 수 있었으며, 4회차부터 활성화되어 높은 순도의 생성물이 얻어지는 것을 알 수 있다.As can be seen in Table 2, it was confirmed that the catalyst was not completely activated until the third reaction, and it was found that the product of high purity was obtained after activation from the fourth cycle.
실시예Example 1: One: 전처리된Preprocessed 세라믹 고체 촉매를 이용한 지방산 Fatty acids using ceramic solid catalysts 메틸methyl 에스테르 생산 Ester production
대두유 50ml, 올레인산 50ml를 혼합한 전처리액을 비커에 담아 60℃까지 가열한 후 여기에 실시예 1에서 제조한 세라믹 고체 촉매 20g을 넣고 12시간동안 교반한 후 고체 촉매를 꺼내어 상온에서 2시간 방치하여 전처리된 고체 촉매를 제조하였다. 50 ml of soybean oil and 50 ml of oleic acid were charged in a beaker and heated to 60 ° C. After 20 g of the ceramic solid catalyst prepared in Example 1 was added thereto and stirred for 12 hours, the solid catalyst was taken out and left at room temperature for 2 hours A pretreated solid catalyst was prepared.
전처리된 고체 촉매를 사용하여 비교예 1에서와 동일한 조건에서 지방산 메틸 에스테르 생산 실험을 수행하고, 그 결과를 하기 표 3에 나타내었다. The pretreated solid catalyst was used to conduct experiments for the production of fatty acid methyl esters under the same conditions as in Comparative Example 1, and the results are shown in Table 3 below.
표 3에서 보는 것과 같이, 전처리한 촉매를 사용한 경우 촉매가 조기에 활성화되어 1회차 반응부터 높은 순도의 지방산 메틸 에스테르를 얻을 수 있었다.As shown in Table 3, when the pretreated catalyst was used, the catalyst was activated early and a high purity fatty acid methyl ester could be obtained from the first reaction.
실시예Example 2: 전처리액의 친수성 물질 함량에 따른 세라믹 고체 촉매의 활성 평가 2: Evaluation of the Activity of Ceramic Solid Catalysts according to the Amount of Hydrophilic Substance in Pretreatment Solution
대두유 50ml와 올레인산 50ml를 혼합한 전처리액에 친수성 물질로 메탄올을 0~50% 첨가하여 세라믹 고체 촉매를 전처리한 후 비교예 1과 동일한 조건에서 메틸 에스테르 생산 실험을 수행하고, 그 결과를 하기 표 4에 나타내었다. The pretreatment of the ceramic solid catalyst was carried out by adding 0 to 50% methanol as a hydrophilic substance to the pretreatment liquid obtained by mixing 50 ml of soybean oil and 50 ml of oleic acid, and then conducting the experiment of producing methyl ester under the same conditions as in Comparative Example 1 , Respectively.
표 4에서 보는 것과 같이 수용성 물질인 메탄올의 함량이 높아질수록 전처리 효과가 낮아지는 것을 확인하였다. As shown in Table 4, it was confirmed that the pretreatment effect was lowered as the content of methanol as a water-soluble material was increased.
이상에서 설명한 바와 같이, 본 발명이 속하는 기술분야의 통상의 기술자는 다양하게 변형된 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 상술한 실시 예들은 모든 면에 예시적인 것이며 한정적인 것이 아닌 것으로서 이해해야만 한다. 본 발명의 범위는 상세한 설명보다는 후술하는 특허등록청구범위에 의하여 나타내어지며, 특허등록청구범위의 의미 및 범위 그리고 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.As described above, it will be appreciated that those of ordinary skill in the art to which the present invention pertains can be embodied in various modified forms. It is therefore to be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined by the appended claims, rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and equivalents of the claims are to be construed as being included within the scope of the present invention do.
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| KR19990014874A (en) * | 1995-07-18 | 1999-02-25 | 야마모또 가즈모또 | Catalyst for preparing carboxylic ester |
| US20110054200A1 (en) * | 2009-09-01 | 2011-03-03 | Catilin, Inc. | Systems and Processes for Biodiesel Production |
| KR20130077844A (en) * | 2010-06-01 | 2013-07-09 | 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 | Hydroprocessing catalysts and their production |
| KR20100138860A (en) * | 2010-11-23 | 2010-12-31 | (주)에스엠피오티 | Ceramic catalyst used for manufacturing fatty acid alkyl-group ester and method thereof using same |
| KR20150007412A (en) * | 2013-07-10 | 2015-01-21 | 한국생산기술연구원 | Cushioning article for automobile interior |
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