TW202003104A - Method for producing fatty acid esters thereof - Google Patents
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本發明利用錳-鋁固體金屬氧化物，作為觸媒製備脂肪酸酯的方法，特別是以油脂與多元醇、異構醇或多碳醇的轉酯化與交換酯化的反應，有效提升其轉化率和脂肪酸酯產率，作為製備脂肪酸酯的方法。 The present invention uses manganese-aluminum solid metal oxide as a catalyst to prepare fatty acid esters, especially by the transesterification and exchange esterification reactions of fats and oils with polyhydric alcohols, isomeric alcohols or multi-carbon alcohols to effectively improve their Conversion rate and fatty acid ester yield are used as a method for preparing fatty acid esters.
天然油脂主要是由脂肪酸與甘油所構成之化學結構，包含游離脂肪酸(free fatty acid,FFA)、單酸甘油酯(MG)、二酸甘油酯(DG)與三酸甘油酯(TG)，其中又以三酸甘油酯的含量最高。一般市售的食用油是經過溶劑萃油→蒸餾(作為去除溶劑)→脫膠(作為去除磷酸脂)→脫酸(用以去除游離脂肪酸)→水洗→脫色→脫臭等多道化工精煉製程，最後才能生產出符合食品級的精緻食用油。目前已發現的天然脂肪酸有800種以上，其中以12-24個碳鏈結構最常見。脂肪酸依結構可簡單分為飽和脂肪酸(saturated fatty acid)、單不飽和脂肪酸(monounsaturated fatty acid，只有一個雙鍵)與多不飽和脂肪酸(polyunsaturated fatty acid，二個雙鍵以上)，而一般脂肪酸的表示方法可利用碳數與雙鍵數量來標示，例如：硬脂酸(stearic acid)為18個碳的飽和脂肪酸，可標示為C18：0，依此類推，油酸(oleic acid)為C18：1，亞麻油酸(Linoleic acid)為C18：2，次亞麻油酸(Linolenic acid)為C18：3。 Natural oils and fats are mainly composed of fatty acids and glycerol, including free fatty acids (FFA), monoglycerides (MG), diglycerides (DG) and triglycerides (TG), of which The content of triglyceride is the highest. Generally, the commercially available edible oil is subjected to multiple chemical refining processes such as solvent extraction → distillation (as solvent removal) → degumming (as phosphate removal) → deacidification (to remove free fatty acids) → water washing → decolorization → deodorization, etc. Only then can we produce refined edible oils that meet the food grade. More than 800 kinds of natural fatty acids have been discovered so far, with 12-24 carbon chain structures being the most common. Fatty acids can be divided into saturated fatty acids (saturated fatty acids), monounsaturated fatty acids (only one double bond) and polyunsaturated fatty acids (more than two double bonds) according to the structure, and general fatty acids The method of expression can be marked by the number of carbons and the number of double bonds. For example, stearic acid is a 18-carbon saturated fatty acid, which can be marked as C18:0, and so on, and oleic acid is C18: 1. Linoleic acid is C18:2, and Linolenic acid is C18:3.
許多醫學研究顯示，不飽和脂肪酸可降低高密度膽固醇，進而減少高血壓、中風、心臟病等疾病發生機率，同時在維護生物膜的結構和功能方面有重要作用，因此已廣泛應用於醫藥、營養補充劑、保健食品等領域，例如：從魚油中萃取EPA(Eicosa-Pentaenoic Acid，二十碳五烯酸)與DHA(Docosa-Hexaenoic Acid，二十二碳六烯酸)，可作為保健食品使用。然而，不飽和脂肪酸因雙鍵性質活潑、不穩定，容易受到外在環境(例如：光、熱、溫度、氧氣)而發生聚合、裂解、氧化等反應，因此在產品純化分離過程中需特別留意，避免發生變質而降低產品收率。 Many medical studies have shown that unsaturated fatty acids can reduce high-density cholesterol, thereby reducing the incidence of hypertension, stroke, heart disease and other diseases. At the same time, they have an important role in maintaining the structure and function of biofilms, so they have been widely used in medicine and nutrition Supplements, health foods and other fields, such as: extracting EPA (Eicosa-Pentaenoic Acid, eicosapentaenoic acid) and DHA (Docosa-Hexaenoic Acid, docosahexaenoic acid) from fish oil, can be used as health food . However, unsaturated fatty acids are active and unstable due to the double bond nature, and are susceptible to polymerization, cracking, oxidation and other reactions caused by external environment (such as light, heat, temperature, oxygen), so special attention should be paid to the product purification and separation process , To avoid deterioration and reduce product yield.
目前不飽和脂肪酸主要分離技術有低溫結晶、尿素包合、分子蒸餾、超臨界萃取等技術。傳統製程是將油脂先經高溫高壓的水解製程，經純化分離後獲得混合的脂肪酸與甘油；混合的脂肪酸可再純化以取得特定結構的脂肪酸。脂肪酸再與醇類在酸性觸媒下進行酯化反應生成脂肪酸酯，但酯化為可逆反應，需使用脫水劑/夾帶劑移除水分來提高反應轉化率與脂肪酸酯的產率。因此，傳統脂肪酸酯的生產需油脂水解製程與酯化製程二步驟生產流程，以及繁複的純化分離單元。 At present, the main separation technologies of unsaturated fatty acids include low-temperature crystallization, urea inclusion, molecular distillation, supercritical extraction and other technologies. In the traditional process, fats and oils are firstly subjected to a high-temperature and high-pressure hydrolysis process. After purification and separation, mixed fatty acids and glycerin are obtained; the mixed fatty acids can be further purified to obtain fatty acids with specific structures. Fatty acids are then esterified with alcohols under acidic catalysts to produce fatty acid esters, but esterification is a reversible reaction. Dehydration agents/entrainers are required to remove moisture to increase the reaction conversion rate and the yield of fatty acid esters. Therefore, the production of traditional fatty acid esters requires a two-step production process of fat hydrolysis process and esterification process, and a complicated purification and separation unit.
先前技術中，參考美國專利公告號US 7842653 B2，其中Srinivas等人曾揭露以鐵-鋅氰化物作為觸媒，以高壓釜生產脂肪酸辛酯作為生質潤滑油應用，轉化率90-96%；但其生產方法為批次式製程，反應時間較長(3-6小時)，觸媒可能大量溶出污染產品，醇類僅為烷基單元醇。 In the prior art, refer to US Patent Publication No. US 7842653 B2, in which Srinivas et al. have disclosed the use of iron-zinc cyanide as a catalyst and the production of fatty acid octyl ester in an autoclave as a raw oil, with a conversion rate of 90-96%; However, the production method is a batch process, the reaction time is longer (3-6 hours), the catalyst may elute a large amount of contaminated products, and the alcohols are only alkyl unit alcohols.
先前技術中，參考美國專利公告號US 8124801 B2，其中Srinivas等人又揭露以固體酸性觸媒(Mo-P-Ca-Al氧化物)作為觸媒，同樣以高壓釜生產脂肪酸甲酯(生質柴油)與脂肪酸辛酯，產率分別為89.7%與91.2%；但其生產方法一樣為批次式製程，反應時間較長(8小時)，觸媒可 能溶出污染產品，醇類僅為烷基單元醇。 In the prior art, refer to US Patent Publication No. US 8124801 B2, in which Srinivas et al. disclosed that solid acid catalyst (Mo-P-Ca-Al oxide) was used as the catalyst, and fatty acid methyl ester (biomass) was also produced by autoclave. Diesel) and fatty acid octyl ester, the yields are 89.7% and 91.2% respectively; but the production method is the same batch process, the reaction time is longer (8 hours), the catalyst may dissolve the contaminated product, the alcohol is only alkyl Unit alcohol.
先前技術中，參考美國專利公告號US 8962873 B2，其中Summers等人以前述觸媒(Mo-P-Al氧化物)進行連續式生產測試，脂肪酸甲酯產率為99%，以脂肪酸甲酯再與辛醇反應生成脂肪酸辛酯，產率為93.5%；但反應時間較長(WHSV為0.4-0.7h-1)(WHSV：Weight hourly space velocity，WHSV=油脂進料質量流速/觸媒質量)，觸媒可能溶出污染產品與觸媒壽命短之疑慮，醇類僅為烷基單元醇。 In the prior art, refer to US Patent Publication No. US 8962873 B2, in which Summers et al. conducted continuous production testing with the aforementioned catalyst (Mo-P-Al oxide), and the yield of fatty acid methyl ester was 99%. It reacts with octanol to produce fatty acid octyl ester with a yield of 93.5%; but the reaction time is longer (WHSV is 0.4-0.7h -1 ) (WHSV: Weight hourly space velocity, WHSV=grease feed mass flow rate/catalyst quality) As the catalyst may dissolve the contaminated product and the catalyst has a short lifespan, the alcohols are only alkyl unit alcohols.
先前技術中，參考中華民國專利證號I590868，其專利為固體金屬氧化觸媒之製備及其在轉酯化反應之應用，曾提出以固體金屬氧化觸媒進行轉酯化反應產生一脂肪酸烷基酯，其中該醇類係為甲醇、乙醇、丙醇、丁醇或多元醇，然而根據I590868揭示的方法，將該方法應用於部分的直鏈烷基單元醇、異構化單元醇、二元醇或多元醇(甘油)的轉酯化反應時，仍會遇到轉化率以及脂肪酸產率較差的情形。 In the prior art, refer to the Republic of China Patent No. I590868, whose patent is the preparation of solid metal oxidation catalyst and its application in transesterification reaction. It has been proposed to use a solid metal oxidation catalyst for transesterification to produce a fatty acid alkyl group Ester, wherein the alcohol is methanol, ethanol, propanol, butanol or polyhydric alcohol, but according to the method disclosed in I590868, the method is applied to part of linear alkyl unit alcohol, isomerized unit alcohol, binary In the transesterification of alcohols or polyhydric alcohols (glycerol), the conversion rate and fatty acid yield are still poor.
承上所述，先前技術普遍面臨觸媒溶出造成產品汙染且縮短觸媒壽命等問題。另外，先前技術所使用的反應物之醇類多為烷基單元醇，即便依照先前技術所揭示的內容，又即使提高了反應器溫度與壓力，對於多元醇、異構化醇或多碳醇(n≧4)仍無法有效提升其轉化率和脂肪酸酯產率。 As mentioned above, the prior art is generally faced with the problems of catalyst contamination, product contamination and shortened catalyst life. In addition, the alcohols of the reactants used in the prior art are mostly alkyl unit alcohols. Even if the temperature and pressure of the reactor are increased according to the content disclosed in the prior art, for polyols, isomerized alcohols or multi-carbon alcohols (n≧4) still cannot effectively improve its conversion rate and fatty acid ester yield.
有鑑於此，本發明針對先前技術之缺失進行改良，針對觸媒性能進行提升，以實現可與多數的醇類進行轉酯化反應之方法。本發明提供一種利用錳-鋁固體金屬氧化觸媒進行轉酯化反應之方法，以油脂與醇類為原料，可有效提升其轉化率和脂肪酸酯產率，且反應物之醇類可為 甲醇、正丙醇、正丁醇、正辛醇、月桂醇、異丙醇、異丁醇、異戊醇、2-乙基己醇、乙二醇、分子量200的聚乙二醇(PEG200)、分子量400的聚乙二醇(PEG400)、1,3-丙二醇、1,2-丙二醇或甘油。 In view of this, the present invention improves on the deficiencies of the prior art and improves the performance of the catalyst, so as to realize the method of transesterification with most alcohols. The invention provides a method for transesterification reaction using a manganese-aluminum solid metal oxidation catalyst. The fat and alcohol are used as raw materials, which can effectively improve the conversion rate and fatty acid ester yield, and the alcohol of the reactant can be Methanol, n-propanol, n-butanol, n-octanol, lauryl alcohol, isopropanol, isobutanol, isoamyl alcohol, 2-ethylhexanol, ethylene glycol, polyethylene glycol with a molecular weight of 200 (PEG200) , Polyethylene glycol with molecular weight of 400 (PEG400), 1,3-propanediol, 1,2-propanediol or glycerin.
利用錳-鋁固體金屬氧化觸媒，在適當反應條件下，以反應溫度為180-300℃，反應壓力為40-90bar，反應物滯留時間為60-100分鐘，反應空間速度為0.4-1.0hr-1，採取二段式反應，可使轉化率達92%以上，脂肪酸酯產率達70%以上；金屬溶出量<50ppm。 Using manganese-aluminum solid metal oxidation catalyst, under appropriate reaction conditions, the reaction temperature is 180-300°C, the reaction pressure is 40-90bar, the residence time of the reactants is 60-100 minutes, and the reaction space velocity is 0.4-1.0hr -1 , adopting two-stage reaction, the conversion rate can reach more than 92%, the yield of fatty acid ester can reach more than 70%; the amount of metal dissolution <50ppm.
本發明旨在提供一種錳-鋁固體金屬氧化觸媒在轉酯化反應之方法，包括：a)將二個以上之金屬化合物依一金屬化合物比例均勻混合，經一擠壓成型方法與一高溫鍛燒方法後形成該錳-鋁固體金屬氧化觸媒，再將該錳-鋁固體金屬氧化觸媒填充於一固定床反應器中，以進行轉酯化反應；b)利用該錳-鋁固體金屬氧化觸媒進行一第一段轉酯化反應產生一第一產物，其中包括將一反應物以一反應條件進行反應，該反應物包含一醇類及一油脂類，該反應條件包括在該固定床反應器中設置一反應溫度、一反應壓力、一反應物滯留時間以及一反應空間速度，該反應溫度為180-300℃，該反應壓力為40-90bar，該反應物滯留時間為60-100分鐘，該反應空間速度為0.4-1.0hr-1；c)利用該錳-鋁固體金屬氧化觸媒進行一第二段轉酯化反應產生一第二產物，其中包括將該第一產物以該反應條件進行反應，其中該第二產物包含一脂肪酸烷基酯。 The invention aims to provide a method for transesterification reaction of a manganese-aluminum solid metal oxidation catalyst, which includes: a) mixing two or more metal compounds uniformly in proportion of a metal compound, through an extrusion molding method and a high temperature After the calcination method, the manganese-aluminum solid metal oxidation catalyst is formed, and then the manganese-aluminum solid metal oxidation catalyst is filled in a fixed bed reactor for transesterification; b) using the manganese-aluminum solid The metal oxidation catalyst performs a first-stage transesterification reaction to produce a first product, which includes reacting a reactant under a reaction condition, the reactant includes an alcohol and a fat, and the reaction condition is included in the A reaction temperature, a reaction pressure, a reactant residence time and a reaction space velocity are set in the fixed bed reactor. The reaction temperature is 180-300°C, the reaction pressure is 40-90 bar, and the reactant residence time is 60- 100 minutes, the reaction space velocity is 0.4-1.0hr -1 ; c) a second-stage transesterification reaction using the manganese-aluminum solid metal oxidation catalyst produces a second product, which includes the first product The reaction is carried out under the reaction conditions, wherein the second product comprises a fatty acid alkyl ester.
如上所述之第一段轉酯化反應與所述之第二段轉酯化反 應，具有相同的反應條件。 The first-stage transesterification reaction described above has the same reaction conditions as the second-stage transesterification reaction described above.
較佳地，所述反應物之該醇類與該油脂類具有一醇油莫耳比，其中醇油莫耳比為2-30。 Preferably, the alcohol and the oil of the reactant have a molar ratio of alcohol to oil, wherein the molar ratio of alcohol to oil is 2-30.
較佳地，該醇類包括多元醇、異構化醇或多碳醇(n≧4)。 Preferably, the alcohols include polyhydric alcohols, isomerized alcohols or multi-carbon alcohols (n≧4).
較佳地，該醇類包括正丙醇、正丁醇、正辛醇、異丙醇、異戊醇、1,2-丙二醇、1,3-丙二醇、2-乙基己醇、分子量200的聚乙二醇(PEG200)或分子量400的聚乙二醇(PEG400)。 Preferably, the alcohols include n-propanol, n-butanol, n-octanol, isopropanol, isoamyl alcohol, 1,2-propanediol, 1,3-propanediol, 2-ethylhexanol, and a molecular weight of 200 Polyethylene glycol (PEG200) or 400 molecular weight polyethylene glycol (PEG400).
較佳地，該油脂類包括大豆油、痲瘋樹籽油、蓖麻油、桐油、棕櫚油、椰子油、油酸(oleic acid)、豬油、牛油、藻油、廢食用油或廢酸油。 Preferably, the oils and fats include soybean oil, jatropha seed oil, castor oil, tung oil, palm oil, coconut oil, oleic acid, lard, tallow, algal oil, waste edible oil or waste acid oil.
較佳地，透過本發明揭示之方法，可使得轉酯化反應之轉化率達92%以上，脂肪酸酯產率達70%以上。 Preferably, through the method disclosed in the present invention, the conversion rate of the transesterification reaction can be more than 92%, and the yield of fatty acid ester can be more than 70%.
較佳地，透過本發明揭示之方法，可使得轉酯化反應之金屬溶出量<50ppm。 Preferably, through the method disclosed in the present invention, the metal dissolution amount of the transesterification reaction can be made <50 ppm.
較佳地，該錳-鋁固體金屬氧化觸媒係為球型(ball)、圓柱型(cylinder)、三瓣型(threelobe)、四瓣型(quadrolobe)、半環型(semi-ring)，該錳-鋁固體金屬氧化觸媒外徑介於1-3mm之間。 Preferably, the manganese-aluminum solid metal oxidation catalyst system is a ball type, a cylinder type, a three-lobed type (threelobe), a quad-lobed type (quadrolobe), a semi-ring type (semi-ring), The outer diameter of the manganese-aluminum solid metal oxidation catalyst is between 1-3mm.
較佳地，該高溫鍛燒方法之溫度為350-1200℃，並持溫1小時以上，再將溫度降至室溫。 Preferably, the temperature of the high-temperature calcination method is 350-1200°C, and the temperature is maintained for more than 1 hour, and then the temperature is lowered to room temperature.
第1圖為本方法發明之實施步驟流程圖。 Figure 1 is a flow chart of the implementation steps of the method invention.
第2圖為本發明方法測試多種油脂料源之測試結果。 Figure 2 is the test result of the method of the present invention for testing various oil and fat sources.
第3圖為本發明方法長時間生產測試之測試結果。 Figure 3 shows the test results of the long-term production test of the method of the present invention.
第4圖為本方法發明第一段反應實施於異構化烷基單元醇之反應結果。 Figure 4 is the result of the reaction of the isomerization of alkyl unit alcohol in the first stage of the method invention.
第5圖為本方法發明第一段反應實施於異構化烷基單元醇之反應結果。 Figure 5 is the reaction result of the isomerization of alkyl unit alcohol in the first stage reaction of the method invention.
第6圖為本方法發明第一段反應實施於二元醇和多元醇之反應結果。 Figure 6 is the result of the reaction of the first stage of the method invention on the diol and polyol.
為利貴審查委員了解本發明之技術特徵、內容與優點及其所能達到之功效，茲將本發明配合附圖，並以實施例之表達形式詳細說明如下，而其中所使用之圖式，其主旨僅為示意及輔助說明書之用，未必為本發明實施後之真實比例與精準配置，故不應就所附之圖式的比例與配置關係解讀、侷限本發明於實際實施上的權利範圍，合先敘明。 In order to facilitate your review committee to understand the technical features, contents and advantages of the present invention and the effects it can achieve, the present invention is described in detail in conjunction with the drawings and in the form of expressions of the embodiments, and the drawings used therein, which The main purpose is only for illustration and auxiliary description, not necessarily the true proportion and precise configuration after the implementation of the present invention, so the proportion and configuration relationship of the attached drawings should not be interpreted and limited to the scope of the present invention in practical implementation. He Xianming.
本發明方法之步驟流程如第1圖所示，其中各步驟之實施請參閱以下實施例。 The steps of the method of the present invention are shown in FIG. 1, and the implementation of each step please refer to the following embodiments.
觸媒製備：將3g氧化錳與27g的水合氧化鋁(pseudo-boehmite)均勻混和，添加適量的水混和攪拌，以擠壓成型機(extruder)製成圓柱狀，經室溫乾燥24小時後，再以高溫爐鍛燒，持溫在550℃、4小時，再降到室溫。最後可獲得直徑1-2mm，長度3-10mm之觸媒。 Catalyst preparation: Mix 3g of manganese oxide with 27g of hydrated alumina (pseudo-boehmite) uniformly, add an appropriate amount of water to mix and stir, and make it into a cylindrical shape with an extruder. After drying at room temperature for 24 hours, It is then calcined in a high-temperature furnace, held at 550°C for 4 hours, and then lowered to room temperature. Finally, a catalyst with a diameter of 1-2 mm and a length of 3-10 mm can be obtained.
第一段轉酯化反應：醇類與油脂分別經由高壓幫浦系統 推動進入連續式固定床反應器(ID*L=23.8mm*600mm)，系統配有溫度與進料流速自動控制設備，以及一個背壓閥裝置控制系統壓力。將75.6g的觸媒填充於反應器中段，反應器上、下段以1mm的玻璃珠填充。反應進料為大豆油與甲醇，加熱器溫度230℃(反應器內溫度185℃)，壓力68bar，醇油莫耳比25-30，WHSV為1.0(h-1)，滯留時間約60-80分鐘。產品經冷凝器冷卻後收集，並以氣相層析火焰離子化偵檢器(GC-FID)分析，可得轉化率為100%，脂肪酸甲酯產率為99.4%。 The first stage of transesterification: alcohols and oils are pushed into the continuous fixed bed reactor (ID*L=23.8mm*600mm) through the high-pressure pump system, the system is equipped with automatic temperature and feed flow control equipment, and A back pressure valve device controls the system pressure. 75.6g of catalyst was filled in the middle section of the reactor, and the upper and lower sections of the reactor were filled with 1mm glass beads. The reaction feed is soybean oil and methanol, the temperature of the heater is 230°C (185°C in the reactor), the pressure is 68 bar, the molar ratio of alcohol to oil is 25-30, the WHSV is 1.0 (h -1 ), and the residence time is about 60-80. minute. The product was collected after cooling by the condenser and analyzed by gas chromatography flame ionization detector (GC-FID). The conversion rate was 100%, and the yield of fatty acid methyl ester was 99.4%.
使用與實施例二相同實驗設備與觸媒，以正丙醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度228℃)，壓力68bar，醇油莫耳比15-20，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為66.6%，脂肪酸正丙酯產率為60.2%。因收集的產物為均勻的液相，直接再當進料進行反應(第二段轉酯化反應)，可得轉化率為96.8%，脂肪酸正丙酯產率為95.0%。 Using the same experimental equipment and catalyst as in Example 2, n-propanol was reacted with soybean oil feed, the operating conditions were
使用與實施例二相同實驗設備與觸媒，以正丁醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度227℃)，壓力68bar，醇油莫耳比10-15，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為64.6%，脂肪酸正丁酯產率為58.9%。因收集的產物為均勻的液相，直接再當進料進行反應(第二段轉酯化反應)，可得轉化率為96.8%，脂肪酸正丁酯產率為93.9%。 Using the same experimental equipment and catalyst as in Example 2, using n-butanol to react with soybean oil feed, the operating conditions are
使用與實施例二相同實驗設備與觸媒，以正辛醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度218℃)，壓力68bar，醇油莫耳比6-10，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為94.9%，脂肪酸正辛酯產率為93.8%。因收集的產物為均勻的液相，直接再當進料進行反應(第二段轉酯化反應)，可得轉化率為98.6%，脂肪酸正辛酯產率為97.6%。 Using the same experimental equipment and catalyst as in Example 2, n-octanol is reacted with soybean oil feed, the operating conditions are
使用與實施例二相同實驗設備與觸媒，以月桂醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度232℃)，壓力68bar，醇油莫耳比3-6，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為91.5%，月桂醇脂肪酸酯產率為89.9%。 Using the same experimental equipment and catalyst as in Example 2, using lauryl alcohol to react with soybean oil feed, the operating conditions are
使用與實施例二相同實驗設備與觸媒，以異丙醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度218℃)，壓力68bar，醇油莫耳比15-20，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為48.9%，脂肪酸異丙酯產率為37.9%。因收集的產物為均勻的液相，直接再當進料進行反應(第二段轉酯化反應)，可得轉化率為98.2%，脂肪酸異丙酯產率為71.0%。 Using the same experimental equipment and catalyst as in Example 2, isopropyl alcohol was reacted with soybean oil feed. The operating conditions were
使用與實施例二相同實驗設備與觸媒，以異丁醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度218℃)，壓力68bar，醇油莫耳比10-15，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉 化率為71.5%，脂肪酸異丁酯產率為66.6%。 Using the same experimental equipment and catalyst as in Example 2, isobutanol was reacted with soybean oil feed. The operating conditions were
使用與實施例二相同實驗設備與觸媒，以異戊醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度218℃)，壓力68bar，醇油莫耳比10-15，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為71.6%，脂肪酸異戊酯產率為66.8%。因收集的產物為均勻的液相，直接再當進料進行反應(第二段轉酯化反應)，可得轉化率為93.9%，脂肪酸異戊酯產率為91.2%。 Using the same experimental equipment and catalyst as in Example 2, using isoamyl alcohol to react with soybean oil feed, the operating conditions are
使用與實施例二相同實驗設備與觸媒，以2-乙基己醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度225℃)，壓力68bar，醇油莫耳比6-10，WHSV為1.0(h-1)，可得轉化率為74.1%，脂肪酸2-乙基己酯產率為71.4%。 Using the same experimental equipment and catalyst as in Example 2, 2-ethylhexanol was reacted with soybean oil feed. The operating conditions were
使用與實施例二相同實驗設備與觸媒，以乙二醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度243℃)，壓力68bar，醇油莫耳比10-15，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為86.7%，脂肪酸乙二醇單酯產率為76.7%。 The same experimental equipment and catalyst as in Example 2 were used to react ethylene glycol with soybean oil feed. The operating conditions were a heater temperature of 290°C (reactor temperature of 243°C), a pressure of 68 bar, and an alcohol oil molar ratio of 10- 15. WHSV is 1.0 (h -1 ), the residence time is about 60-80 minutes, the available conversion rate is 86.7%, and the yield of fatty acid ethylene glycol monoester is 76.7%.
使用與實施例二相同實驗設備與觸媒，以分子量200的聚乙二醇(PEG200)與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度252℃)，壓力68bar，醇油莫耳比5-8，WHSV為1.0(h-1)，滯留時間 約60-80分鐘，可得轉化率為98.1%，脂肪酸PEG200單酯產率為57.0%。 Using the same experimental equipment and catalyst as in Example 2, polyethylene glycol (PEG200) with a molecular weight of 200 was used to react with soybean oil feed. The operating conditions were a heater temperature of 290°C (reactor temperature of 252°C) and a pressure of 68 bar. The molar ratio of alcohol to oil is 5-8, the WHSV is 1.0 (h -1 ), the residence time is about 60-80 minutes, the available conversion rate is 98.1%, and the yield of fatty acid PEG200 monoester is 57.0%.
使用相同實驗設備與觸媒，以分子量400的聚乙二醇(PEG400)與大豆油進料反應，操作條件為加熱器溫度270℃(反應器內溫度245℃)，壓力68bar，醇油莫耳比2-6，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為94.6%，脂肪酸PEG400單酯產率為43.5%。 Using the same experimental equipment and catalyst, polyethylene glycol (PEG400) with a molecular weight of 400 was used to react with soybean oil feed. The operating conditions were
使用與實施例二相同實驗設備與觸媒，以1,3-丙二醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度232℃)，壓力68bar，醇油莫耳比10-15，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為96.3%，脂肪酸1,3-丙二醇單酯產率為87.4%。因收集的產物為均勻的液相，直接再當進料進行反應(第二段轉酯化反應)，可得轉化率為100%，脂肪酸1,3-丙二醇單酯產率為97.5%。 Using the same experimental equipment and catalyst as Example 2, 1,3-propanediol was reacted with soybean oil feed, the operating conditions were
使用與實施例二相同實驗設備與觸媒，以1,2-丙二醇與大豆油進料反應，操作條件為加熱器溫度290℃(反應器內溫度227℃)，壓力68bar，醇油莫耳比10-15，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉化率為99.8%，脂肪酸1,2-丙二醇單酯產率為92.4%。 Using the same experimental equipment and catalyst as in Example 2, 1,2-propanediol was reacted with soybean oil feed, the operating conditions were
使用與實施例二相同實驗設備與觸媒，以甘油與大豆油進料反應，操作條件為加熱器溫度270℃(反應器內溫度235℃)，壓力68bar，醇油莫耳比6-10，WHSV為1.0(h-1)，滯留時間約60-80分鐘，可得轉 化率為39.9%，單酸甘油酯產率為17.6%，二酸甘油酯產率為14.6%，合計脂肪酸酯(單酸甘油酯+二酸甘油酯)產率為32.2%。 Using the same experimental equipment and catalyst as in Example 2, glycerol was reacted with soybean oil feed, the operating conditions were
本實施例為本發明方法進一步測試多種油脂料源，測試結果顯示揭示的生物油脂料源皆可使用，但進料的酸價與含水量有所限制，一般而言，建議酸價<10mgKOH/g(相當於游離脂肪酸FFA含量小於5wt.%)；含水量小於0.1wt.%。請參閱第2圖，測試的油脂料源包括大豆油、痲瘋樹油、蓖麻油、桐油、棕櫚油、椰子油和廢食用油，該些測試反應條件為反應溫度190℃、壓力90bar、WHSV為1.0(h-1)，滯留時間約60-80分鐘，此處測試之廢食用油，酸價為8.54mgKOH/g。 This embodiment is a method of the present invention to further test a variety of oil and fat sources. The test results show that the disclosed biological oil and fat sources can be used, but the acid value and water content of the feed are limited. In general, the recommended acid value is <10mgKOH/ g (equivalent to free fatty acid FFA content less than 5wt.%); water content is less than 0.1wt.%. Please refer to Figure 2. The tested oil sources include soybean oil, jatropha oil, castor oil, tung oil, palm oil, coconut oil and waste edible oil. The reaction conditions for these tests are reaction temperature 190℃, pressure 90bar, WHSV It is 1.0 (h -1 ) and the residence time is about 60-80 minutes. The acid value of the waste edible oil tested here is 8.54 mgKOH/g.
使用與實施例一相同觸媒，實驗設備與實施例二相似，但反應器設計為一連續式二段反應器串聯，以2-乙基己醇與棕櫚油進料反應，操作條件為反應器內溫度240℃，壓力60bar，醇油莫耳比20-27，WHSV為0.34(h-1)，每段反應器的滯留時間約40-50分鐘，可得轉化率為99.6%，脂肪酸2-乙基己酯產率為99.1%。 The same catalyst as in Example 1 is used, and the experimental equipment is similar to that in Example 2, but the reactor is designed as a continuous two-stage reactor in series, 2-ethylhexanol is reacted with palm oil feed, and the operating conditions are the reactor The internal temperature is 240℃, the pressure is 60 bar, the molar ratio of alcohol to oil is 20-27, the WHSV is 0.34 (h -1 ), the residence time of each reactor is about 40-50 minutes, the conversion rate is 99.6%, the fatty acid 2- The ethylhexyl ester yield was 99.1%.
使用與實施例十八相同觸媒與實驗設備，以1,2-丙二醇與棕櫚油進料反應，操作條件為反應器內溫度240℃，壓力60bar，醇油莫耳比20-27，WHSV為0.44(h-1)，每段反應器的滯留時間約30-40分鐘，可得轉化率為98.1%，脂肪酸酯產率為96.6%。 Using the same catalyst and experimental equipment as in Example 18, 1,2-propanediol was reacted with palm oil feed, the operating conditions were a reactor temperature of 240°C, a pressure of 60 bar, an alcohol-oil molar ratio of 20-27, and WHSV of 0.44 (h -1 ), the residence time of each reactor is about 30-40 minutes, the available conversion rate is 98.1%, and the yield of fatty acid ester is 96.6%.
使用與實施例十八相同觸媒與實驗設備，以PEG400與棕櫚油進料反應，操作條件為反應器內溫度250℃，壓力60bar，醇油莫耳比2-6，WHSV為0.44(h-1)，每段反應器的滯留時間約40-50分鐘，可得轉化率為91.8%，脂肪酸酯產率為89.5%。 18 cases using the same catalyst and experimental apparatus embodiment, the feed to the reaction of palm oil and PEG400, operating conditions within the
脂肪酸酯長時間生產測試：請參閱第3圖，相同觸媒，調整適當操作條件，即可生產不同脂肪酸酯，且觸媒仍維持絕佳活性。初期的產率波動是測試不同實驗參數(溫度、壓力、醇油比、LHSV)，目的是找到最佳之操作條件，觸媒測試達5388小時仍維持高活性。 Long-term production test of fatty acid esters: Please refer to Figure 3, the same catalyst, adjust the appropriate operating conditions, you can produce different fatty acid esters, and the catalyst still maintains excellent activity. The initial yield fluctuation is to test different experimental parameters (temperature, pressure, alcohol to oil ratio, LHSV), the purpose is to find the best operating conditions, the catalyst test up to 5388 hours still maintain high activity.
請參閱第4-6圖，進一步分析本發明實施於不同醇類料源之測試結果。 Please refer to Figures 4-6 to further analyze the test results of the present invention implemented on different alcohol sources.
請參閱第4圖，為本發明第一段反應實施於直鏈烷基單元醇之反應結果，雖然在甲醇反應性仍為最佳(產率~90%)，但是同樣的也發現丙醇與丁醇最差(產率~80%)，而辛醇與月桂醇又變好(產率~90%)。 Please refer to Fig. 4 for the reaction result of the first-stage reaction of the present invention carried out on a linear alkyl unit alcohol. Although the reactivity in methanol is still the best (yield ~90%), but also found that propanol and Butanol is the worst (yield ~80%), while octanol and lauryl alcohol are better (yield ~90%).
請參閱第5圖，為本發明第一段反應實施於異構化烷基單元醇之反應結果，隨著碳數越高，脂肪酸酯(FAE)的轉化率與產率也越高。異構化單元醇較直鏈烷基單元醇反應性來的差(相同碳數下比較)，推測可能是分子的立體障礙造成反應下降。 Please refer to FIG. 5 for the reaction result of the isomerization of alkyl unit alcohol in the first stage of the present invention. As the carbon number is higher, the conversion rate and yield of fatty acid ester (FAE) are higher. Isomerized unit alcohols have poorer reactivity than linear alkyl unit alcohols (compared at the same carbon number), presumably because of steric obstacles in the molecule that caused the reaction to decline.
請參閱第6圖，為本發明第一段反應實施於二元醇和多元醇(甘油)之反應結果，比較乙二醇(n=1)、PEG200(n=4-5)、PEG400(n=8- 9)，n值越大，脂肪酸酯(FAE)的產率越低(77-51%)。再比較乙二醇與丙二醇，碳數較大的丙二醇其脂肪酸酯(FAE)的產率較高，而1,2-丙二醇又比1,3-丙二醇反應性來的佳。 Please refer to Figure 6 for the results of the first stage reaction of the present invention carried out on the reaction of glycol and polyol (glycerol), comparing ethylene glycol (n=1), PEG200 (n=4-5), PEG400 (n= 8-9), the larger the value of n, the lower the yield of fatty acid ester (FAE) (77-51%). Comparing ethylene glycol and propylene glycol, propylene glycol with a larger carbon number has a higher fatty acid ester (FAE) yield, and 1,2-propanediol has better reactivity than 1,3-propanediol.
請參閱表1，為本發明各項實施例之第一段轉酯化反應的反應條件及反應數據。 Please refer to Table 1 for the reaction conditions and reaction data of the first stage transesterification reaction in various embodiments of the present invention.
請參閱表2，為本發明各項實施例之第一段及第二段轉酯化反應條件及反應數據，由此可知，經由本發明揭示之二段式反應，相較於先前技術能有效提升轉酯化反應之轉化率和脂肪酸酯產率。 Please refer to Table 2 for the first stage and second stage transesterification reaction conditions and reaction data of various embodiments of the present invention. It can be seen that the two-stage reaction disclosed by the present invention is more effective than the prior art Improve the conversion rate and fatty acid ester yield of transesterification.
雖然上文實施方式中揭露了本發明的具體實施例，然其並非用以限定本發明，本發明所屬技術領域中具有通常知識者，在不悖離本發明之原理與精神的情形下，當可對其進行各種更動與修飾，因此本發明之保護範圍當以附隨申請專利範圍所界定者為準。 Although the above embodiments disclose specific examples of the present invention, they are not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention belongs, without departing from the principle and spirit of the present invention, should Various changes and modifications can be made to it, so the scope of protection of the present invention shall be defined by the scope of the accompanying patent application.
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|---|---|---|---|---|
| EP2197995A4 (en) * | 2007-11-22 | 2011-06-15 | Nippon Catalytic Chem Ind | Method for producing fatty acid alkyl esters and/or glycerin using fat or oil |
| TWI590868B (en) * | 2014-06-06 | 2017-07-11 | 台灣中油股份有限公司 | Solid metal oxide catalyst application on the transesterification and interesterification reactions |
-
2018
- 2018-05-24 TW TW107117773A patent/TWI650173B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| TWI650173B (en) | 2019-02-11 |
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