TWI599649B - Solid base catalyst for manufacturing biodiesel, fabricating method thereof and manufacturing method of biodiesel using thereof - Google Patents
Solid base catalyst for manufacturing biodiesel, fabricating method thereof and manufacturing method of biodiesel using thereof Download PDFInfo
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本發明係有關於一種用於製造生質柴油之固體鹼觸媒,尤其是有關於一種利用鋰鹽製備並可用以製造生質柴油之固體鹼觸媒、其製備方法及應用其之生質柴油製造方法。 The present invention relates to a solid base catalyst for producing biodiesel, in particular to a solid base catalyst prepared by using a lithium salt and capable of producing biodiesel, a preparation method thereof and a biodiesel using the same Production method.
石化燃料是目前世界上最普遍的動力來源,且其在工業發展、交通運輸以及農業發展都佔據著很重要的地位,進而提升人類的生活品質使得生活能夠更加便利。然而,隨著全世界快速增加的人口,石化燃料的使用量也開始大幅增加,但其產量有限是個長久以來的隱憂。再者,石化燃料長期存在的問題,如無法重複使用、空氣污染、開採不易、價格不穩等亦難以獲得解決。 Petrochemical fuel is currently the most common source of power in the world, and it plays an important role in industrial development, transportation and agricultural development, and thus enhances the quality of human life and makes life more convenient. However, with the rapidly increasing population of the world, the use of fossil fuels has begun to increase substantially, but its limited production is a long-standing concern. Moreover, the long-standing problems of fossil fuels, such as the inability to reuse, air pollution, mining, and price instability, are difficult to solve.
相較之下,生質能中的生質柴油具有與化石柴油相近的性質,且這種燃料具有減少汙染物的排放及對健康 的影響、生物可分解性、無毒、不含硫、燃燒後產生的氣體汙染性低以及儲存安全等優點,被視為是既經濟又具潛力的能源替代方案之一。 In contrast, biodiesel in biomass has similar properties to fossil diesel, and this fuel has reduced pollutant emissions and health. Its impact, biodegradability, non-toxicity, sulfur-free, low gas pollution from combustion and safe storage are considered to be both economical and potential energy alternatives.
生質柴油的製造方式主要分為化學催化和生物催化,其中化學鹼催化因具有高轉酯率、反應時間短等優點,是目前使用較廣的技術。而用於化學鹼催化之觸媒包括液體類及固體類,當中固體鹼觸媒因具有易分離、可回收等特點,較受業界歡迎。目前常見用於製造生質柴油的固體鹼觸媒有氧化鈣、碳酸鋰等,然而氧化鈣的空氣穩定度差,易吸收空氣中的水份與二氧化碳而失效,且氧化鈣顆粒較大表面積較小,整體轉酯率偏低。而碳酸鋰之鹼性強度較弱,因此轉酯效果欠佳。 The production methods of biodiesel are mainly divided into chemical catalysis and biocatalysis. Among them, chemical base catalysis is a widely used technology due to its high transesterification rate and short reaction time. The catalyst used for chemical base catalysis includes liquids and solids. Among them, solid base catalysts are popular in the industry because of their easy separation and recyclability. At present, solid base catalysts commonly used in the manufacture of biodiesel have calcium oxide, lithium carbonate, etc. However, calcium oxide has poor air stability, easily absorbs moisture in the air and carbon dioxide, and has a larger surface area of calcium oxide particles. Small, the overall transesterification rate is low. The basic strength of lithium carbonate is weak, so the transesterification effect is not good.
另一方面,隨著全球的經濟開發、都市化與公共建設的推動,各種事業發展所衍生出來的廢棄物,除了可能佔用大量的土地外,也須耗費巨額的清運或處理費用,不但造成了環境負荷也相對地影響環境品質。 On the other hand, with the development of global economic development, urbanization and public construction, wastes derived from various business developments, in addition to occupying a large amount of land, also cost huge amounts of transportation or disposal costs, which not only causes Environmental load also affects environmental quality relatively.
有鑑於此,若能有效地利用各種事業廢棄物製備生質柴油製造過程中所需之固體鹼觸媒,不但能減輕廢棄物處理的負擔,又能降低購買固體鹼觸媒之成本,同時又有助於提供能量來源,可謂一舉數得。 In view of this, the effective use of various commercial wastes to prepare solid alkali catalysts required for the production of biodiesel can not only reduce the burden of waste disposal, but also reduce the cost of purchasing solid alkali catalysts. It helps to provide a source of energy.
有鑑於此,本發明之一態樣在於提供一種用於製造生質柴油之固體鹼觸媒,係包含由下列化學式表示之化合物:LiaXbOc,其中X為鈦、鋁、鋯、釩、鈮、鉬、鎢、硼、鉍、錳、銅、鎳、鉻、鋅或鈷,a為1至6之正整數,b為1至4之正整數以及c為1至7之正整數。 In view of the above, an aspect of the present invention provides a solid base catalyst for producing biodiesel, which comprises a compound represented by the following chemical formula: Li a X b O c , wherein X is titanium, aluminum, zirconium, Vanadium, ruthenium, molybdenum, tungsten, boron, ruthenium, manganese, copper, nickel, chromium, zinc or cobalt, a is a positive integer from 1 to 6, b is a positive integer from 1 to 4, and c is a positive integer from 1 to 7. .
依據前述態樣之一實施例,固體鹼觸媒包含鋁酸鋰、鈦酸鋰、鋯酸鋰、鉍酸鋰、鈮酸鋰、偏鈮酸鋰、次鈮酸鋰、焦鈮酸鋰、正釩酸鋰、偏釩酸鋰、次釩酸鋰、鎢酸鋰、過氧鎢酸鋰、鉬酸鋰、過氧鉬酸鋰、硼酸鋰、偏硼酸鋰、鉻酸鋰、錳酸鋰、鈷酸鋰、亞鈷酸鋰、鎳酸鋰、鋅酸鋰、銅酸鋰或亞銅酸鋰。 According to one embodiment of the foregoing aspect, the solid base catalyst comprises lithium aluminate, lithium titanate, lithium zirconate, lithium niobate, lithium niobate, lithium metasilicate, lithium hypophosphite, lithium pyroantimonate, and Lithium vanadate, lithium metavanadate, lithium hypovanadate, lithium tungstate, lithium peroxytungstate, lithium molybdate, lithium peroxodimolybdate, lithium borate, lithium metaborate, lithium chromate, lithium manganate, cobalt Lithium acid, lithium cobaltite, lithium nickelate, lithium zincate, lithium copperate or lithium cuprous citrate.
本發明之另一態樣在於提供一種用於製造生質柴油之固體鹼觸媒之製備方法,包含步驟(a)提供第一固體反應物作為鋰源、步驟(b)混合第一固體反應物與第二固體反應物以得到混合物,其中第二固體反應物包含鋁源或鈦源以及步驟(c)熱處理混合物以獲得固體鹼觸媒。 Another aspect of the present invention provides a method for preparing a solid base catalyst for producing biodiesel, comprising the steps of: (a) providing a first solid reactant as a lithium source, and step (b) mixing a first solid reactant. The second solid reactant is used to obtain a mixture, wherein the second solid reactant comprises an aluminum source or a titanium source and the step (c) heat-treating the mixture to obtain a solid base catalyst.
依據前述態樣之一實施例,第一固體反應物係純鋰、鋰合金、硝酸鋰、碳酸鋰、氫氧化鋰、氧化鋰、鋰輝石、鋰雲母或透鋰長石。 According to one embodiment of the foregoing aspect, the first solid reactant is pure lithium, lithium alloy, lithium nitrate, lithium carbonate, lithium hydroxide, lithium oxide, spodumene, lithium mica or lithium feldspar.
依據前述態樣之另一實施例,第二固體反應物更包含鋯源、釩源、鈮源、鉬源、鎢源、硼源、鉍源、錳源、銅源、鎳源、鋅源、鉻源或鈷源。第二固體反應物可以是鋁 礬土、鋁箔片、鋁鎂合金、鈦鋁合金、高溫爐隔熱磚、坩堝、廢觸媒、回收電池、廢五金、煉鋼廠爐渣、含鈦污泥、廢磚塊、瓦片、瓷器、陶器、鋯英石、硼酸鹽、硼矽酸鹽礦、含釩廢催化劑、鉭鈮精礦、鎢鋼或天然泥土及其製品。 According to another embodiment of the foregoing aspect, the second solid reactant further comprises a zirconium source, a vanadium source, a germanium source, a molybdenum source, a tungsten source, a boron source, a germanium source, a manganese source, a copper source, a nickel source, a zinc source, Chromium source or cobalt source. The second solid reactant may be aluminum Bauxite, aluminum foil, aluminum-magnesium alloy, titanium-aluminum alloy, high-temperature furnace insulation brick, concrete, waste catalyst, recycled battery, scrap metal, steel slag, titanium-containing sludge, waste brick, tile, porcelain , pottery, zircon, borate, borosilicate ore, vanadium-containing spent catalyst, antimony concentrate, tungsten steel or natural clay and its products.
藉此,本發明可利用上述天然物或固體廢料作為第二固體反應物製備固體鹼觸媒,使得地球有限的資源能夠物盡其用並符合現今環保標準。 Thereby, the present invention can utilize the above-mentioned natural or solid waste as a second solid reactant to prepare a solid alkali catalyst, so that the limited resources of the earth can be utilized to the best and meet the current environmental standards.
依據前述態樣之又一實施例,步驟(b)更包含下列步驟。首先,提供含有上述混合物之溶液,隨後烘乾溶液。較佳地,在步驟(b)中第一固體反應物對第二固體反應物之莫耳比為1:5至5:1。 According to still another embodiment of the foregoing aspect, step (b) further comprises the following steps. First, a solution containing the above mixture is provided, followed by drying the solution. Preferably, the molar ratio of the first solid reactant to the second solid reactant in step (b) is from 1:5 to 5:1.
依據前述態樣之再一實施例,步驟(c)係將前述混合物於空氣環境中進行煅燒。較佳地,步驟(c)之溫度係700℃至1000℃,而時間可以持續0.5小時至4小時。另外,步驟(c)更包含將上述混合物研磨成粉體之步驟。 According to still another embodiment of the foregoing aspect, the step (c) is to calcine the aforementioned mixture in an air environment. Preferably, the temperature of step (c) is from 700 ° C to 1000 ° C, and the time may last from 0.5 hours to 4 hours. Further, the step (c) further comprises the step of grinding the above mixture into a powder.
本發明之又一態樣在於提供一種生質柴油之製造方法,包含步驟(I)提供固體鹼觸媒,且步驟(I)包含步驟(a)提供第一固體反應物作為鋰源、步驟(b)混合第一固體反應物與第二固體反應物以得到混合物,其中第二固體反應物包含鋁源或鈦源及步驟(c)熱處理上述混合物以獲得固體鹼觸媒、步驟(II)將油脂與醇類混合並加熱回流,且添加固體鹼觸媒以進行轉酯化反應、步驟(III)使轉酯化反應之生成物分離,並取出酯液以及步驟(IV)真空蒸餾酯液以去除酯液中之殘留醇類與殘留水份,以獲得生質柴油。 Another aspect of the present invention provides a method for producing a biodiesel comprising the step (I) of providing a solid base catalyst, and the step (I) comprising the step (a) of providing a first solid reactant as a lithium source, the step ( b) mixing the first solid reactant with the second solid reactant to obtain a mixture, wherein the second solid reactant comprises an aluminum source or a titanium source and step (c) heat treating the mixture to obtain a solid base catalyst, step (II) The fat and oil are mixed with the alcohol and heated under reflux, and a solid base catalyst is added to carry out the transesterification reaction, the step (III) is used to separate the product of the transesterification reaction, and the ester liquid is taken out and the ester liquid is vacuum distilled in the step (IV). The residual alcohol and residual water in the ester liquid are removed to obtain biodiesel.
依據前述態樣之一實施例,步驟(II)中油脂對醇類之莫耳比為1:6至1:36。 According to one embodiment of the foregoing aspect, the molar ratio of fat to alcohol in step (II) is from 1:6 to 1:36.
藉此,將本發明製備之固體鹼觸媒應用於製造生質柴油上,除廢料的回收利用外,亦有提升轉酯化反應之轉酯率的效果,符合工業上大量製造之需求。 Thereby, the solid base catalyst prepared by the invention is applied to the manufacture of biodiesel, and in addition to the recycling of the waste, the effect of increasing the transesterification rate of the transesterification reaction is met, which meets the demand for mass production in the industry.
S100、S102、S104‧‧‧步驟 S100, S102, S104‧‧‧ steps
S200、S202、S204、S206‧‧‧步驟 S200, S202, S204, S206‧‧‧ steps
為讓本發明之上述和其他目的、特徵與優點能更明顯易懂,所附圖式之說明如下:第1圖係繪示本發明用於製造生質柴油之固體鹼觸媒的製備方法流程圖;第2圖係繪示本發明生質柴油之製造方法流程圖;第3A圖係繪示本發明實驗例1中以不同碳酸鋰對氧化鋁莫耳比所製備之固體鹼觸媒的X射線繞射分析結果;第3B圖係繪示本發明實驗例1中以不同碳酸鋰對氧化鋁莫耳比所製備之固體鹼觸媒的電子顯微鏡影像圖;第3C圖係繪示本發明實驗例1中以不同碳酸鋰對氧化鋁莫耳比製備之固體鹼觸媒對轉酯化反應之轉酯率關係圖;第3D圖係繪示固定第3A圖至第3C圖中碳酸鋰對氧化鋁莫耳比並以不同煅燒溫度所製備之固體鹼觸媒的X射線繞射分析結果;第3E圖係繪示第3D圖之固體鹼觸媒對轉酯化反應的轉酯率關係圖; 第3F圖係固定第3A圖至第3C圖中碳酸鋰對氧化鋁莫耳比並以不同煅燒時間所製備之固體鹼觸媒的X射線繞射分析結果;第3G圖係繪示第3F圖之固體鹼觸媒對轉酯化反應的轉酯率關係圖;第4A圖係本發明實驗例1中以鋁礬土作為第二固體反應物時以不同碳酸鋰對鋁礬土莫耳比所製備之固體鹼觸媒對轉酯化反應之轉酯率關係圖;第4B圖係本發明實驗例1中以鋁礬土作為第二固體反應物時以不同煅燒溫度所製備之固體鹼觸媒對轉酯化反應之轉酯率關係圖圖;第4C圖係本發明實驗例1中以鋁礬土作為第二固體反應物時以不同煅燒時間所製備之固體鹼觸媒對轉酯化反應之轉酯率關係圖;第5A圖係本發明實驗例2中以不同碳酸鋰對二氧化鈦莫耳比所製備之固體鹼觸媒的X射線繞射分析結果;第5B圖係本發明實驗例2中以不同碳酸鋰對二氧化鈦莫耳比所製備之固體鹼觸媒對轉酯化反應之轉酯率關係圖;第5C圖係固定第5A圖之碳酸鋰對二氧化鈦莫耳比並以不同煅燒溫度所製備之固體鹼觸媒的X射線繞射分析結果;第5D圖係第5C圖之固體鹼觸媒對轉酯化反應的轉酯率關係圖;第5E圖係固定第5A圖之碳酸鋰對二氧化鈦莫耳比並以不同煅燒時間所製備之固體鹼觸媒的X射線繞射分析結果; 第5F圖係第5E圖之固體鹼觸媒對轉酯化反應的轉酯率關係圖;以及第5G圖係本發明實驗例2中以碳酸鋰與二氧化鈦所製備之固體鹼觸媒之重複使用次數對轉酯率的關係圖。 The above and other objects, features and advantages of the present invention will become more apparent and understood. The description of the drawing is as follows. FIG. 1 is a flow chart showing the preparation method of the solid base catalyst for producing biodiesel according to the present invention. Figure 2 is a flow chart showing the manufacturing method of the biodiesel of the present invention; and Figure 3A is a diagram showing the X of the solid base catalyst prepared by different lithium carbonate to alumina molar ratio in Experimental Example 1 of the present invention. The results of the ray diffraction analysis; FIG. 3B is an electron microscope image of the solid base catalyst prepared by using different lithium carbonate to alumina molar ratio in Experimental Example 1 of the present invention; FIG. 3C is a view showing the experiment of the present invention Example 1 shows the relationship between the transesterification of the solid base catalyst prepared by different lithium carbonate to alumina molar ratio in the transesterification reaction; the 3D figure shows the fixation of the lithium carbonate to the oxidation in the 3A to 3C X-ray diffraction analysis results of solid molar catalyst prepared by aluminum molar ratio and prepared at different calcination temperatures; FIG. 3E is a diagram showing the relationship of transesterification of solid base catalyst to transesterification reaction in FIG. 3D; The 3F figure is an X-ray diffraction analysis result of fixing the solid base catalyst prepared by the lithium carbonate to alumina molar ratio and the different calcination time in the 3A to 3C drawings; the 3G drawing shows the 3F drawing Diagram of the transesterification ratio of the solid base catalyst to the transesterification reaction; FIG. 4A shows the different molar ratio of lithium carbonate to the bauxite molar in the experimental example 1 of the present invention using bauxite as the second solid reactant. The relationship between the prepared solid base catalyst and the transesterification rate of the transesterification reaction; FIG. 4B is the solid base catalyst prepared by the different calcination temperature when the bauxite is used as the second solid reactant in the experimental example 1 of the present invention. Fig. 4C is a diagram showing the transesterification of a solid base catalyst prepared by different calcination times when bauxite is used as the second solid reactant in Experimental Example 1 of the present invention. FIG. 5A is a result of X-ray diffraction analysis of a solid base catalyst prepared by using different lithium carbonate to titanium dioxide molar ratio in Experimental Example 2 of the present invention; FIG. 5B is an experimental example 2 of the present invention. Transesterification of solid base catalyst prepared by different lithium carbonate to titanium dioxide molar ratio The relationship of the transesterification ratio is shown in Fig. 5C. The X-ray diffraction analysis results of the solid base catalyst prepared by fixing the lithium carbonate to the titanium dioxide molar ratio of Fig. 5A and different calcination temperatures; 5DFig. 5C Diagram of the relationship between the transesterification rate of the solid base catalyst on the transesterification reaction; Figure 5E is the X-ray diffraction of the solid base catalyst prepared by fixing the lithium carbonate to the titanium dioxide molar ratio of Figure 5A and prepared by different calcination times. Shooting analysis results; 5F is a diagram showing the relationship between the transesterification ratio of the solid base catalyst to the transesterification reaction in FIG. 5E; and the 5G diagram is the repeated use of the solid alkali catalyst prepared by the lithium carbonate and the titanium dioxide in the experimental example 2 of the present invention. The relationship between the number of times and the transesterification rate.
承上,本發明旨在提供一種用於製造生質柴油之固體鹼觸媒。上述固體鹼觸媒包含LiaXbOc、NaaXbOc、KaXbOc中任一者之化合物,其中X為鈦、鋁、鋯、釩、鈮、鐵、鉬、鎢、硼、鉍、鈷、鉻、錳、鎳、銅或鋅,a為1至6之正整數,b為1至4之正整數以及c為1至7之正整數。 The present invention is directed to providing a solid base catalyst for the manufacture of biodiesel. The solid base catalyst comprises a compound of any one of Li a X b O c , Na a X b O c , and K a X b O c , wherein X is titanium, aluminum, zirconium, vanadium, niobium, iron, molybdenum, Tungsten, boron, lanthanum, cobalt, chromium, manganese, nickel, copper or zinc, a is a positive integer from 1 to 6, b is a positive integer from 1 to 4, and c is a positive integer from 1 to 7.
依據本發明之一實施例,固體鹼觸媒之成份可以為鋁酸鋰(LiAlO2)、鈦酸鋰(Li2TiO3)、鋯酸鋰(Li2ZrO3)、鉍酸鋰(LiBiO3)、鈮酸鋰(Li3NbO4)、偏鈮酸鋰(LiNbO3)、次鈮酸鋰(LiNbO2)、焦鈮酸鋰(Li4Nb2O7)、正釩酸鋰(Li3VO4)、偏釩酸鋰(LiVO3)、次釩酸鋰(LiVO2)、鎢酸鋰(Li2WO4)、過氧鎢酸鋰(Li6WO6)、鉬酸鋰(Li2MoO4)、過氧鉬酸鋰(Li6MoO6)、四硼酸鋰(Li2B4O7)、偏硼酸鋰(LiBO2)、鉻酸鋰(LiCrO2或Li3CrO4)、錳酸鋰(Li2MnO3,LiMnO2)、鈷酸鋰(LiCoO2)、亞鈷酸鋰(Li6CoO4)、鎳酸鋰(Li2NiO2或LiNiO2)、銅酸鋰(Li2CuO2)、亞銅酸鋰(LiCuO)、鋅酸鋰(Li2ZnO2)、鈦酸鈉(Na2TiO3)、鈦酸鉀(K2TiO3)、鋯酸鈉(Na2ZrO3)、鋯酸鉀(K2ZrO3)、鉍酸鈉(NaBiO3)、鉍酸鉀 (KBiO3)、鈮酸鈉(Na3NbO4)、鈮酸鉀(K3NbO4)、偏鈮酸鈉(NaNbO3)、偏鈮酸鉀(KNbO3)、焦鈮酸鈉(Na4Nb2O7)、焦鈮酸鉀(K4Nb2O7)、正釩酸納(Na3VO4)、正釩酸鉀(K3VO4)、偏釩酸鈉(NaVO3)、偏釩酸鉀(KVO3)、次釩酸鈉(NaVO2)、次釩酸鉀(KVO2)、鐵酸鈉(NaFeO2)、亞鐵酸鈉(Na2FeO2)、過氧鐵酸鈉(Na2FeO4)、鐵酸鉀(K2FeO4)、亞鐵酸鉀(K2FeO2)、過氧鐵酸鉀(KFeO2)、鎢酸鈉(Na2WO4)、鎢酸鉀(K2WO4)、過氧鎢酸鈉(Na6WO6)、過氧鎢酸鉀(K6WO6)、鉬酸鈉(Na2MoO4)、鉬酸鉀(K2MoO4)、過氧鉬酸鈉(Na6MoO6)、過氧鉬酸鉀(K6MoO6)、四硼酸鈉(Na2B4O7)、四硼酸鉀(K2B4O7)、鈷酸鈉(NaCoO2)、亞鈷酸鈉(Na2CoO2)、鈷酸鉀(KCoO2)、亞鈷酸鉀(K2CoO2)、鎳酸鈉(Na2NiO2)、鎳酸鉀(K2NiO2)、銅酸鈉(Na2CuO2)、銅酸鉀(K2CuO2)、亞銅酸鈉(NaCuO)、亞銅酸鉀(KCuO)、鋅酸鈉(Na2ZnO2)、鋅酸鉀(K2ZnO2)、鉻酸鈉(NaCrO2或Na3CrO3)、鉻酸鉀(KCrO2或K3CrO3)、錳酸鈉(Na2MnO3或NaMnO2)或錳酸鉀(K2MnO3或KMnO2)。 According to an embodiment of the present invention, the solid base catalyst may be composed of lithium aluminate (LiAlO 2 ), lithium titanate (Li 2 TiO 3 ), lithium zirconate (Li 2 ZrO 3 ), lithium niobate (LiBiO 3 ). Lithium niobate (Li 3 NbO 4 ), lithium metasilicate (LiNbO 3 ), lithium niobate (LiNbO 2 ), lithium pyroantimonate (Li 4 Nb 2 O 7 ), lithium orthovanadate (Li 3 ) VO 4 ), lithium metavanadate (LiVO 3 ), lithium pentoxide (LiVO 2 ), lithium tungstate (Li 2 WO 4 ), lithium peroxytungstate (Li 6 WO 6 ), lithium molybdate (Li 2 ) MoO 4 ), lithium peroxodimolybdate (Li 6 MoO 6 ), lithium tetraborate (Li 2 B 4 O 7 ), lithium metaborate (LiBO 2 ), lithium chromate (LiCrO 2 or Li 3 CrO 4 ), manganese Lithium acid (Li 2 MnO 3 , LiMnO 2 ), lithium cobaltate (LiCoO 2 ), lithium cobaltite (Li 6 CoO 4 ), lithium nickelate (Li 2 NiO 2 or LiNiO 2 ), lithium copperate (Li 2 ) CuO 2 ), lithium cuprousate (LiCuO), lithium zincate (Li 2 ZnO 2 ), sodium titanate (Na 2 TiO 3 ), potassium titanate (K 2 TiO 3 ), sodium zirconate (Na 2 ZrO 3 ) ), zirconium potassium (K 2 ZrO 3), sodium bismuthate (NaBiO 3), bismuth potassium (KBiO 3), sodium niobate (Na 4), potassium niobate 3 NbO (K 3 NbO 4) , metaniobate sodium (NaNbO 3), partial potassium niobate (KNbO 3), sodium niobate pyrophosphate (Na 4 Nb 2 O 7) Coke potassium niobate (K 4 Nb 2 O 7) , sodium n-vanadate (Na 4 3 VO), potassium orthovanadate (K 3 VO 4), sodium metavanadate (3 NaVO), potassium metavanadate (the KVO 3 ), sodium hypovanadate (NaVO 2 ), potassium hypovanadate (KVO 2 ), sodium ferrite (NaFeO 2 ), sodium ferrite (Na 2 FeO 2 ), sodium peroxyferrate (Na 2 FeO 4 ) ), potassium ferrite (K 2 FeO 4 ), potassium ferrite (K 2 FeO 2 ), potassium peroxoferrate (KFeO 2 ), sodium tungstate (Na 2 WO 4 ), potassium tungstate (K 2 WO 4 ), sodium peroxytungstate (Na 6 WO 6 ), potassium peroxytungstic acid (K 6 WO 6 ), sodium molybdate (Na 2 MoO 4 ), potassium molybdate (K 2 MoO 4 ), peroxy molybdenum Sodium (Na 6 MoO 6 ), potassium peroxo molybdate (K 6 MoO 6 ), sodium tetraborate (Na 2 B 4 O 7 ), potassium tetraborate (K 2 B 4 O 7 ), sodium cobaltate (NaCoO) 2 ), sodium cobaltite (Na 2 CoO 2 ), potassium cobaltate (KCoO 2 ), potassium cobaltite (K 2 CoO 2 ), sodium nickelate (Na 2 NiO 2 ), potassium nickelate (K 2 NiO) 2 ), sodium c02 (Na 2 CuO 2 ), potassium citrate (K 2 CuO 2 ), sodium cuprous (NaCuO), potassium citrate (KCuO), sodium zincate (Na 2 ZnO 2 ), zinc Potassium (K 2 ZnO 2 ), sodium chromate (NaCrO 2 or Na 3 CrO 3 ), potassium chromate (KCrO 2 or K 3 CrO 3 ), sodium manganate (Na 2 MnO 3 or NaMnO 2 ) Or potassium manganate (K 2 MnO 3 or KMnO 2 ).
本發明進一步提供上述固體鹼觸媒的製備方法,請參考第1圖,第1圖係繪示本發明一實施例中用於製造生質柴油之固體鹼觸媒的製備方法流程圖,用於製造生質柴油之固體鹼觸媒的製備方法包含步驟S100、步驟S102和步驟S104。 The present invention further provides a method for preparing the above solid base catalyst. Please refer to FIG. 1 . FIG. 1 is a flow chart showing a method for preparing a solid base catalyst for producing biodiesel according to an embodiment of the present invention. The method for preparing a solid base catalyst for producing biodiesel comprises the steps S100, S102 and S104.
首先,如步驟S100所示,提供第一固體反應物。依據本發明一實施例,第一固體反應物係包含鹼金族元素,且較佳為鋰源、鈉源與鉀源。進一步來說,鋰源可以為純鋰、鋰合金、硝酸鋰(LiNO3)、碳酸鋰(Li2CO3)、氫氧化鋰(LiOH)、氧化鋰(Li2O)、鋰輝石、鋰雲母或透鋰長石,鈉源可以為碳酸鈉(Na2CO3)、氧化鈉(Na2O)、鈉長石(NaAlSi3O8)、智利硝石(NaNO3)或苛性鈉,而鉀源可以為碳酸鉀(K2CO3)、氫氧化鋰(LiOH)、氧化鉀(K2O)、鉀雲母、鉀長石或鉀明礬。 First, as shown in step S100, a first solid reactant is provided. According to an embodiment of the invention, the first solid reactant system comprises an alkali gold group element, and is preferably a lithium source, a sodium source and a potassium source. Further, the lithium source may be pure lithium, lithium alloy, lithium nitrate (LiNO 3 ), lithium carbonate (Li 2 CO 3 ), lithium hydroxide (LiOH), lithium oxide (Li 2 O), spodumene, lithium mica. Or lithium feldspar, the sodium source may be sodium carbonate (Na 2 CO 3 ), sodium oxide (Na 2 O), albite (NaAlSi 3 O 8 ), Chilean saltpeter (NaNO 3 ) or caustic soda, and the potassium source may be Potassium carbonate (K 2 CO 3 ), lithium hydroxide (LiOH), potassium oxide (K 2 O), potassium mica, potassium feldspar or potassium alum.
接著,混合第一固體反應物與第二固體反應物以得到一混合物,如步驟S102所示。具體而言,在步驟S102中可將第一固體反應物與第二固體反應物分別研磨後再充分混合,或是先混合再研磨,本發明不以此為限。此外,在此步驟中第一固體反應物對第二固體反應物之莫耳比為1:5至5:1,至於兩者間之莫耳比之於固體鹼觸媒之催化效果的影響將揭示於後述實驗例中,在此暫不贅述。 Next, the first solid reactant and the second solid reactant are mixed to obtain a mixture as shown in step S102. Specifically, in step S102, the first solid reactant and the second solid reactant may be separately ground and then mixed thoroughly, or mixed and then ground, and the invention is not limited thereto. In addition, the molar ratio of the first solid reactant to the second solid reactant in this step is 1:5 to 5:1, and the influence of the molar ratio between the two on the catalytic effect of the solid base catalyst will be It will be disclosed in the experimental examples described later, and will not be described here.
承上,第二固體反應物包含鋁源、鈦源、鋯源、釩源、鈮源、鉬源、鎢源、鐵源、硼源、鉍源、鈷源、鉻源、錳源、鎳源、銅源或鋅源。依據本發明之一實施例,第二固體反應物可為前述元素之氧化物、氫氧化物、硝酸鹽或碳酸鹽,如氧化鋁(Al2O3)、二氧化鈦(TiO2)、二氧化鋯(ZrO2)、硝酸鉍(Bi(NO3)3.5H2O)、氧化鉍(Bi2O3)、五氧化二鈮(Nb2O5)、釩酸銨(NH4VO3)、氧化釩(III)(V2O3)、氧化釩(VI)(V2O5)、氧化鐵(Fe2O3)、氧化亞鐵(FeO)、氧化鎢 (WO3)、三氧化鉬(MoO3)、氧化硼(B2O3)、氧化鉻(Cr2O3)、二氧化錳(MnO2)、氫氧化錳(Mn(OH)2)、氧化鈷(Co2O3)、氧化亞鈷(CoO)、氧化鎳(NiO)、氫氧化鎳(Ni(OH)2)、氧化銅(CuO)、氧化亞銅(Cu2O)或氧化鋅(ZnO)。 The second solid reactant comprises an aluminum source, a titanium source, a zirconium source, a vanadium source, a germanium source, a molybdenum source, a tungsten source, an iron source, a boron source, a germanium source, a cobalt source, a chromium source, a manganese source, and a nickel source. , copper source or zinc source. According to an embodiment of the present invention, the second solid reactant may be an oxide, a hydroxide, a nitrate or a carbonate of the foregoing element, such as alumina (Al 2 O 3 ), titania (TiO 2 ), zirconium dioxide. (ZrO 2 ), bismuth nitrate (Bi(NO 3 ) 3 .5H 2 O), bismuth oxide (Bi 2 O 3 ), niobium pentoxide (Nb 2 O 5 ), ammonium vanadate (NH 4 VO 3 ), Vanadium (III) oxide (V 2 O 3 ), vanadium (VI) oxide (V 2 O 5 ), iron oxide (Fe 2 O 3 ), ferrous oxide (FeO), tungsten oxide (WO 3 ), molybdenum trioxide (MoO 3 ), boron oxide (B 2 O 3 ), chromium oxide (Cr 2 O 3 ), manganese dioxide (MnO 2 ), manganese hydroxide (Mn(OH) 2 ), cobalt oxide (Co 2 O 3 ) Cobalt oxide (CoO), nickel oxide (NiO), nickel hydroxide (Ni(OH) 2 ), copper oxide (CuO), cuprous oxide (Cu 2 O) or zinc oxide (ZnO).
此外,前述第二固體反應物的來源係可取材自生活或產業中常見之固體廢料。以鋁源為例,鋁是地球上含量第三多的元素,也是含量最多的金屬,除了鋁礬土為天然泥土而易於取得外,在生活中也有許多應用到鋁的物品。然而,當這些含鋁物品需要淘汰時,就會產生大量的垃圾。藉此,本發明所提供之製備固體鹼觸媒的方法,亦可利用鋁鎂合金、鈦鋁合金或是含鋁廢棄物(如鋁箔片、鋁罐、高溫爐隔熱磚、廢五金、坩堝或廢觸媒)來作為第二固體反應物,以使得地球有限的資源能夠物盡其用,同時亦符合現今環保標準。 In addition, the source of the aforementioned second solid reactant may be obtained from solid waste which is common in life or industry. Taking aluminum source as an example, aluminum is the third most abundant element on the earth, and it is also the most abundant metal. In addition to the easy acquisition of bauxite for natural clay, there are many articles applied to aluminum in life. However, when these aluminum-containing items need to be eliminated, a large amount of garbage is generated. Therefore, the method for preparing a solid alkali catalyst provided by the invention can also utilize aluminum-magnesium alloy, titanium aluminum alloy or aluminum-containing waste (such as aluminum foil, aluminum can, high temperature furnace heat insulation brick, waste hardware, concrete). Or waste catalyst) as the second solid reactant, so that the limited resources of the earth can be used to the best of its ability, and also meet the current environmental standards.
又以鈦源為例,「鈦鐵污泥或礦泥」為生產或提煉二氧化鈦所衍生的廢棄物,其特性為黏稠狀膠體、廢液顏色為深綠色、為強酸且含氯化鐵,多數國家規範為有害事業廢棄物之一種。本發明倘若利用上述含鈦廢棄物作為第二固體反應物,除了可製備用於製造生質柴油之固體鹼觸媒外,進一步亦可達到廢物利用之目的。更甚者,第二固體反應物也可以取自鐵渣、回收電池、煉鋼廠爐渣、廢磚塊、瓦片、瓷器、陶器、鋯英石、硼酸鹽、硼矽酸鹽礦、含釩廢催化劑、鉭鈮精礦、鎢鋼或天然泥土及其製品。 Taking titanium source as an example, "titanium iron sludge or slime" is a waste derived from the production or refining of titanium dioxide. Its characteristics are viscous colloids, the color of waste liquid is dark green, strong acid and iron chloride, most The national standard is a kind of hazardous business waste. In the present invention, in addition to the use of the titanium-containing waste as the second solid reactant, in addition to the preparation of a solid alkali catalyst for the production of biodiesel, the purpose of waste utilization can be further achieved. What's more, the second solid reactant can also be taken from iron slag, recycled batteries, steel slag, waste bricks, tiles, porcelain, pottery, zircon, borate, borosilicate ore, vanadium Waste catalyst, antimony concentrate, tungsten steel or natural clay and its products.
另外,依據本發明之一實施例,步驟S102可更包含對第一固體反應物與第二固體反應物先進行含浸處理(未圖示)。詳細來說,上述處理係先提供含有上述混合物之溶液,亦即將第一固體反應物與第二固體反應物加入至水中再經充分攪拌後形成上述溶液。最後,烘乾上述溶液,藉此達到充分混合以利後續燒結。 In addition, in accordance with an embodiment of the present invention, step S102 may further comprise first impregnation (not shown) of the first solid reactant and the second solid reactant. In detail, the above treatment first provides a solution containing the above mixture, that is, the first solid reactant and the second solid reactant are added to water and then thoroughly stirred to form the above solution. Finally, the above solution is dried, thereby achieving thorough mixing for subsequent sintering.
最後,如步驟S104所示,熱處理上述粉體混合物以獲得固體鹼觸媒。依據本發明之一實施例,步驟S104係一煅燒步驟,且較佳地煅燒步驟之溫度係700℃至1000℃,而時間可以持續0.5小時至4小時,至於煅燒溫度及煅燒時間之於固體鹼觸媒之催化效果的影響將揭示於後述實驗例中,在此暫不贅述。另外,步驟S104可更包含將煅燒後之混合物研磨成粉體之步驟,以使固體鹼觸媒於後續轉酯化反應時能夠均勻分散於油品中,同時更提高固體鹼觸媒之比表面積以提升其於反應中之轉酯率。 Finally, as shown in step S104, the above powder mixture is heat-treated to obtain a solid base catalyst. According to an embodiment of the present invention, step S104 is a calcination step, and preferably the calcination step has a temperature of 700 ° C to 1000 ° C, and the time may last from 0.5 to 4 hours, and the calcination temperature and calcination time are on the solid base. The influence of the catalytic effect of the catalyst will be disclosed in the experimental examples described later, and will not be described herein. In addition, the step S104 may further comprise the step of grinding the calcined mixture into a powder, so that the solid base catalyst can be uniformly dispersed in the oil during the subsequent transesterification reaction, and the specific surface area of the solid alkali catalyst is further increased. In order to increase its transesterification rate in the reaction.
本發明更提供一種利用上述固體鹼觸媒進行轉酯化反應製造生質柴油的方法,如第2圖所示,固體鹼觸媒進行轉酯化反應製造生質柴油的方法包含步驟S200、步驟S202、步驟S204和步驟S206。 The present invention further provides a method for producing biodiesel by transesterification reaction using the above solid base catalyst. As shown in FIG. 2, the method for producing a biodiesel by transesterification of a solid base catalyst comprises the step S200 and the step. S202, step S204 and step S206.
首先,如步驟S200,提供按步驟S100至步驟S104所製備之固體鹼觸媒。接著將油脂及醇類混合並以如65℃加熱回流,同時添加上述固體鹼觸媒以進行轉酯化反應如步驟S202所示。較佳地,上述油脂係指油品中的三酸甘油酯,而油品可為植物油,如大豆油(Soybean oil)、橄 欖油(Olive oil)、玉米油(Cron oil)、芥花油(Canola oil)、椰子油(Coconut oil)、蓖麻油(Castor oil)或可可酯(Cocoa ester),本發明並不欲以此為限。且油品亦可為使用後之廢油,藉此將廢油回收做為燃料使用,相當環保又衛生。另外,上述醇類較佳為甲醇。 First, as step S200, a solid base catalyst prepared in steps S100 to S104 is provided. Next, the fats and oils are mixed and heated under reflux at 65 ° C while the above solid base catalyst is added to carry out the transesterification reaction as shown in step S202. Preferably, the above oil and fat refers to triglyceride in oil, and the oil may be vegetable oil, such as soybean oil, olive. Olive oil, Cron oil, Canola oil, Coconut oil, Castor oil or Cocoa ester, the present invention does not intend to use this Limited. Moreover, the oil can also be the used waste oil, thereby recycling the used oil as a fuel, which is quite environmentally friendly and hygienic. Further, the above alcohol is preferably methanol.
隨後,如步驟S204所示,將轉酯化反應生成之脂肪酸甲酯、甘油及固體鹼觸媒分離。而分離的具體作法例如是先靜置令前述生成物分層後在依序抽離,而分層後的上層酯液為脂肪酸甲酯,其即為可供做為燃料使用之生質柴油。最後,為了純化生質柴油,可再以快速蒸發法或真空蒸餾法去除酯液中的殘留甲醇與水份,如步驟S206所示。 Subsequently, as shown in step S204, the fatty acid methyl ester, glycerin, and solid base catalyst produced by the transesterification reaction are separated. The specific method for the separation is, for example, firstly allowing the aforementioned product to be separated and then sequentially separated, and the layered upper ester liquid is a fatty acid methyl ester, which is a biodiesel which can be used as a fuel. Finally, in order to purify the biomass diesel, the residual methanol and water in the ester liquid may be removed by rapid evaporation or vacuum distillation, as shown in step S206.
此外,更可在進行蒸發或蒸餾前,將上層酯液先水洗數次以儘可能去除上層酯液中的殘留固體鹼觸媒和甘油。有關油醇加熱回流的方式,熟知本領域之技術人員當可依現有技術加以實施,故在此不另行贅述。 Further, the upper ester liquid may be washed with water several times before evaporation or distillation to remove as much as possible of the residual solid base catalyst and glycerin in the upper ester liquid. The manner in which the oleyl alcohol is heated and refluxed is well known to those skilled in the art and can be carried out according to the prior art, and therefore will not be further described herein.
另外,為說明上述固體鹼觸媒於轉酯化反應上之催化效果,合成出的生質柴油會進行轉酯率的鑑定以確定其脂肪酸甲酯的含量,在本研究中是以「經濟部標準檢驗局,CNS15051,油脂衍生物(即脂肪酸甲酯)一總脂肪酸甲酯及次亞麻油酸甲酯含量測定法」進行生質柴油之轉酯率的計算。在此方法中是以十七酸甲酯為內標物,正庚烷為溶劑,將其配置成濃度約10毫克/毫升的溶液,接著精秤純化過之生質柴油250毫克後,再加入配置好之內標物溶液5毫升,並將其均勻混合,便能將其以氣相層析儀進行分析,分 析時使用注射器吸取0.1至1.0μL的樣品注射到氣相層析儀的注射口,接著會以火焰離子偵測器進行分析,分析後所得到之層析圖會對其面積進行積分計算總脂肪酸甲酯的含量。 In addition, in order to explain the catalytic effect of the above solid base catalyst on the transesterification reaction, the synthesized biodiesel will be identified by the transesterification rate to determine the content of the fatty acid methyl ester. In this study, the Ministry of Economy The Standards Inspection Bureau, CNS15051, Oil Derivatives (ie fatty acid methyl esters) - Determination of total fatty acid methyl esters and methyl linoleic acid methyl esters" was used to calculate the transesterification rate of biodiesel. In this method, methyl heptadecanoate is used as an internal standard, n-heptane is used as a solvent, and it is set to a solution having a concentration of about 10 mg/ml, and then 250 mg of the purified diesel oil is purified by a fine scale, and then added. Configure 5 ml of the internal standard solution and mix it evenly, then analyze it by gas chromatography. At the time of analysis, a sample of 0.1 to 1.0 μL is sucked into the injection port of the gas chromatograph using a syringe, and then analyzed by a flame ion detector. The chromatogram obtained after the analysis is integrated to calculate the total fatty acid. The content of methyl ester.
本發明所提供之固體鹼觸媒的組份、其製備方法以及應用其之生質柴油製造方法已大致說明如前文,以下將藉由各個實驗例進一步說明本發明之各步驟、其實驗數據及可達成之功效,惟非用以限制本發明所欲保護之範疇,合先敘明。 The composition of the solid base catalyst provided by the present invention, the preparation method thereof and the method for producing the biodiesel using the same have been roughly described above. The respective steps of the present invention, experimental data thereof and the experimental data thereof will be further described below by using various experimental examples. The achievable effects are not intended to limit the scope of the invention to be protected, and are described first.
實驗例1係以鋰源作為第一固體反應物並以鋁源作為第二固體反應物,而製得之固體鹼觸媒包含鋁酸鋰。 In Experimental Example 1, a lithium source was used as the first solid reactant and an aluminum source was used as the second solid reactant, and the solid base catalyst prepared contained lithium aluminate.
較佳地,第一固體反應物係使用市售試藥級之碳酸鋰(Li2CO3,純度>98%,Katayama Chemical Co.),而第二固體反應物係使用市售試藥級之氧化鋁(Al2O3,純度>99%,Showa Chemical Co.),且製備方法如后。首先,分別取1莫耳的碳酸鋰以及1莫耳的氧化鋁放入燒杯中,並加入100mL的去離子水進行攪拌30分鐘使其均勻混合成一含有碳酸鋰與氧化鋁混合物之溶液。接著,將上述溶液放入烘箱中以120℃烘24小時,再以研缽將烘乾之混合物進行研磨後放入高溫爐(Dengyng instruments CO.LTD,DF-40)內以進行煅燒,其中煅燒溫度為900℃以及煅燒時間為1小時。最後,待上述混合物煅燒完成並降至室溫後, 即可使用研缽進行研磨以獲得可供後續轉酯化反應使用之固體鹼觸媒。 Preferably, the first solid reactant is a commercially available reagent grade lithium carbonate (Li 2 CO 3 , purity > 98%, Katayama Chemical Co.), and the second solid reactant is a commercially available reagent grade. Alumina (Al 2 O 3 , purity >99%, Showa Chemical Co.), and the preparation method is as follows. First, 1 mole of lithium carbonate and 1 mole of alumina were placed in a beaker, and 100 mL of deionized water was added and stirred for 30 minutes to uniformly mix into a solution containing a mixture of lithium carbonate and alumina. Next, the above solution was placed in an oven and baked at 120 ° C for 24 hours, and the dried mixture was ground in a mortar and placed in a high temperature furnace (Dengyng instruments CO. LTD, DF-40) for calcination, wherein calcination was carried out. The temperature was 900 ° C and the calcination time was 1 hour. Finally, after the above mixture is calcined and cooled to room temperature, it can be ground using a mortar to obtain a solid base catalyst for subsequent transesterification.
接下來,本發明改變固體鹼觸媒的各項合成條件如碳酸鋰之莫耳數、固體鹼觸媒之煅燒溫度與煅燒時間等變因以探討上述包含有鋁酸鋰之固體鹼觸媒的較佳合成參數。首先探討改變碳酸鋰之添加用量對合成固體鹼觸媒的影響,固定條件如使用之氧化鋁用量為1莫耳、煅燒溫度900℃、煅燒時間1小時,碳酸鋰的用量則分別為0.25莫耳、0.5莫耳、1莫耳、2莫耳、3莫耳,詳細之合成步驟則參考第1圖及前文所述,在此不再贅述。 Next, the present invention changes various synthesis conditions of the solid base catalyst such as the molar number of lithium carbonate, the calcination temperature of the solid base catalyst, and the calcination time to investigate the above-mentioned solid alkali catalyst containing lithium aluminate. Preferred synthetic parameters. Firstly, the effect of changing the amount of lithium carbonate added on the synthesis of solid base catalyst is discussed. The fixed conditions such as the amount of alumina used are 1 mole, the calcination temperature is 900 ° C, the calcination time is 1 hour, and the amount of lithium carbonate is 0.25 m. 0.5 mu, 1 m, 2 m, 3 m. The detailed synthesis steps are referred to in FIG. 1 and the foregoing, and are not described herein again.
合成出之固體鹼觸媒利用X射線繞射儀(X-Ray Diffractometer,MAC Science,MXP18)測定其成分、利用場發式掃描電子顯微鏡(JEOL,JSM-7401F)觀察其表面形貌、利用比表面積分析儀(Surface Area and Porosity Analyzer,BET)進行比表面積與孔洞結構測定以及進行轉酯率的測定。 The synthesized solid base catalyst was measured for its composition by X-ray Diffractometer (MAC Science, MXP18), and its surface topography and utilization ratio were observed by a field-scanning scanning electron microscope (JEOL, JSM-7401F). The Surface Area and Porosity Analyzer (BET) was used to measure the specific surface area and pore structure and to measure the transesterification rate.
請參考第3A圖至第3C圖,第3A圖係本發明實驗例1中以不同碳酸鋰對氧化鋁莫耳比所製備之固體鹼觸媒的X射線繞射分析結果,第3B圖係本發明實驗例1中以不同碳酸鋰對氧化鋁莫耳比所製備之固體鹼觸媒的電子顯微鏡影像圖,以及第3C圖係本發明實驗例1中以不同碳酸鋰對氧化鋁莫耳比所製備之固體鹼觸媒對轉酯化反應的轉酯率關係圖。 Please refer to FIGS. 3A to 3C. FIG. 3A is an X-ray diffraction analysis result of the solid base catalyst prepared by using different lithium carbonate to alumina molar ratio in Experimental Example 1 of the present invention, and FIG. 3B is a diagram An electron micrograph image of a solid base catalyst prepared by different lithium carbonate to alumina molar ratio in Experimental Example 1 and a 3C graph of different lithium carbonate to alumina molar ratio in Experimental Example 1 of the present invention Diagram of the transesterification rate of the prepared solid base catalyst for the transesterification reaction.
首先,如第3A圖所示,圖中數據由下往上分別是於製備固體鹼觸媒時碳酸鋰對氧化鋁的莫耳比為0.25:1、0.5:1、1:1、2:1與3:1(即碳酸鋰之用量為0.25莫耳、0.5莫耳、1莫耳、2莫耳與3莫耳),且碳酸鋰、氧化鋁、菱形晶相(Rhombohedral)結構之鋁酸鋰(r-LiAlO2)與正方晶相(Tetragonal)結構之鋁酸鋰(t-LiAlO2)分別以空心圓、實心圓、空心三角形與實心三角形來標示。 First, as shown in Fig. 3A, the data in the figure is from bottom to top, respectively, when the solid base catalyst is prepared, the molar ratio of lithium carbonate to alumina is 0.25:1, 0.5:1, 1:1, 2:1. And lithium carbonate, aluminum oxide, rhombohedral structure of lithium aluminate with 3:1 (ie lithium carbonate in an amount of 0.25 m, 0.5 m, 1 m, 2 m and 3 m) (r-LiAlO 2 ) and lithium tetralithate (t-LiAlO 2 ) in a tetragonal phase structure are indicated by hollow circles, filled circles, open triangles and solid triangles, respectively.
其中,當碳酸鋰與氧化鋁之莫耳比為0.25:1時,t-LiAlO2與r-LiAlO2兩種不同晶相的鋁酸鋰均存在於固體鹼觸媒中,且以r-LiAlO2的結晶性較好,但由於添加的碳酸鋰太少,所以仍有殘留的氧化鋁存在。當碳酸鋰與氧化鋁之莫耳比為0.5:1時,由繞射峰可知此時t-LiAlO2的結晶性比r-LiAlO2的結晶性好,但仍有殘留的氧化鋁。當碳酸鋰與氧化鋁之莫耳比為1:1時,由圖中可知此時僅有晶相為t-LiAlO2之鋁酸鋰,至於少許殘留之氧化鋁可推測為藥品秤取時所造成的誤差。當碳酸鋰與氧化鋁之莫耳比為2:1時,由圖中可知此時亦僅有晶相為t-LiAlO2之鋁酸鋰。另外,此時雖沒有殘留之氧化鋁但存在過多未反應完的碳酸鋰存在。當碳酸鋰與氧化鋁之莫耳比為3:1時,t-LiAlO2與r-LiAlO2兩種不同晶相的鋁酸鋰均存在於固體鹼觸媒,且以r-LiAlO2的結晶性較好。另外,由圖可知此時有殘留之碳酸鋰。 Wherein, when the molar ratio of lithium carbonate to alumina is 0.25:1, lithium aluminate of two different crystal phases of t-LiAlO 2 and r-LiAlO 2 are present in the solid base catalyst, and r-LiAlO The crystallinity of 2 is good, but since there is too little lithium carbonate added, residual alumina remains. When the molar ratio of lithium carbonate to alumina is 0.5:1, it is understood from the diffraction peak that the crystallinity of t-LiAlO 2 is better than that of r-LiAlO 2 , but there is still residual alumina. When the molar ratio of lithium carbonate to alumina is 1:1, it can be seen from the figure that only lithium aluminate having a crystal phase of t-LiAlO 2 is present, and a small amount of residual alumina can be presumed to be when the drug is taken. The error caused. When the molar ratio of lithium carbonate to alumina is 2:1, it can be seen from the figure that only lithium aluminate having a crystal phase of t-LiAlO 2 is also present. Further, at this time, although there is no residual alumina, too much unreacted lithium carbonate exists. When the molar ratio of lithium carbonate to alumina is 3:1, lithium aluminate of two different crystal phases of t-LiAlO 2 and r-LiAlO 2 are present in the solid base catalyst, and the crystallinity of r-LiAlO 2 is obtained. better. In addition, it can be seen from the figure that there is lithium carbonate remaining at this time.
鋁酸鋰之表面形貌如第3B圖所示,圖中由左至右、由上而下分別顯示於合成時碳酸鋰對氧化鋁的莫耳比為 0.25:1、0.5:1、1:1、2:1與3:1所製備出之鋁酸鋰的表面形貌。從圖中可以發現,當碳酸鋰的添加用量增加時,其製備而得之固體鹼觸媒表面形貌會逐漸轉為不規則塊狀。 The surface morphology of lithium aluminate is shown in Fig. 3B. The left to right and top to bottom of the graph show the molar ratio of lithium carbonate to alumina during synthesis. The surface morphology of lithium aluminate prepared by 0.25:1, 0.5:1, 1:1, 2:1 and 3:1. It can be seen from the figure that when the amount of lithium carbonate added is increased, the surface morphology of the solid base catalyst prepared by the preparation is gradually changed into an irregular block.
接著,經由比表面積分析儀分析固體鹼觸媒比表面積與孔洞結構的分析結果整理如表1,固體鹼觸媒的比表面積分別為0.9578(0.25莫耳)、0.9811(0.5莫耳)、1.0271(1莫耳)、1.0264(2莫耳)與0.8947(3莫耳)m2/g且其平均孔洞直徑分別為1024.65(0.25莫耳)、973.64(0.5莫耳)、747.29(1莫耳)、549.25(2莫耳)與638.42(3莫耳)Å。由此可知,在本發明中使用不同碳酸鋰用量製備而得之固體鹼觸媒皆屬於巨孔結構,且當碳酸鋰對氧化鋁的莫耳比為1:1時所製備之鋁酸鋰具有最大之的表面積。 Next, the analysis results of the analysis of the specific surface area and the pore structure of the solid base catalyst by the specific surface area analyzer are as shown in Table 1. The specific surface areas of the solid base catalyst were 0.9578 (0.25 m), 0.9811 (0.5 m), and 1.0271, respectively. 1 mole), 1.0264 (2 moles) and 0.8947 (3 moles) m 2 /g and the average pore diameters are 1024.65 (0.25 m), 973.64 (0.5 m), 747.29 (1 m), 549.25 (2 m) and 638.42 (3 m) Å. It can be seen that the solid base catalyst prepared by using different amounts of lithium carbonate in the present invention belongs to a macroporous structure, and the lithium aluminate prepared when the molar ratio of lithium carbonate to alumina is 1:1 has The largest surface area.
隨後,將不同碳酸鋰用量製備之固體鹼觸媒進行轉酯化反應之轉酯率如第3C圖所示,其中固定油醇莫耳比為1:12、固體鹼觸媒用量為6wt%、反應時間為2小時、反應溫度為65℃。必須說明的是,當以實驗例1中包含鋁酸鋰之固體鹼觸媒進行轉酯化反應時,可固定如油醇比(如1:24)、固體鹼觸媒用量(如6wt%)與反應溫度(如65℃)等之相 關反應條件,並改變不同之反應時間以先觀察實驗例1之固體鹼觸媒之最佳轉酯化條件。由下表2可知,實驗例1之固體鹼觸媒係於反應時間2小時下具有最佳之轉酯化效果,故後續將以此條件進行,但本發明不以此為限。 Subsequently, the transesterification ratio of the solid base catalyst prepared by using different amounts of lithium carbonate is shown in FIG. 3C, wherein the fixed oleyl alcohol molar ratio is 1:12, and the solid alkali catalyst is used in an amount of 6 wt%. The reaction time was 2 hours and the reaction temperature was 65 °C. It should be noted that when the transesterification reaction is carried out by the solid base catalyst containing lithium aluminate in Experimental Example 1, it can be fixed such as an oil to alcohol ratio (e.g., 1:24), and a solid base catalyst amount (e.g., 6 wt%). With the reaction temperature (such as 65 ° C) and so on The reaction conditions were changed, and the reaction time was changed to observe the optimum transesterification conditions of the solid base catalyst of Experimental Example 1. It can be seen from the following Table 2 that the solid base catalyst of Experimental Example 1 has the best transesterification effect at the reaction time of 2 hours, and therefore will be carried out under such conditions, but the present invention is not limited thereto.
如第3C圖所示,當碳酸鋰與氧化鋁的莫耳比為0.25:1時,固體鹼觸媒的轉酯率僅有0.90%,而當碳酸鋰與氧化鋁的莫耳比為3:1時其轉酯率則高達97.09%。然而,由第3A圖得知當碳酸鋰與氧化鋁的莫耳比為3:1時所合成之固體鹼觸媒裡殘留有碳酸鋰。 As shown in Fig. 3C, when the molar ratio of lithium carbonate to alumina is 0.25:1, the transesterification ratio of the solid base catalyst is only 0.90%, and when the molar ratio of lithium carbonate to alumina is 3: At 1 o'clock, its transesterification rate was as high as 97.09%. However, it is known from Fig. 3A that lithium carbonate remains in the solid base catalyst synthesized when the molar ratio of lithium carbonate to alumina is 3:1.
接著,進一步探討不同煅燒溫度對於製備而得之固體鹼觸媒的影響,其中固定碳酸鋰對氧化鋁之莫耳比為1:1以及煅燒時間為1小時,煅燒溫度分別以600℃、700℃、800℃、900℃、1000℃進行。請參考第3D圖與第3E圖,第3D圖係繪示固定第3A圖至第3C圖中碳酸鋰對氧化鋁莫耳比並以不同煅燒溫度所製備之固體鹼觸媒的X射線繞射分析結果,第3E圖係繪示第3D圖之固體鹼觸媒對轉酯化反應的轉酯率關係圖。 Next, the effects of different calcination temperatures on the prepared solid base catalyst were further investigated. The molar ratio of fixed lithium carbonate to alumina was 1:1 and the calcination time was 1 hour, and the calcination temperature was 600 ° C and 700 ° C, respectively. It is carried out at 800 ° C, 900 ° C, and 1000 ° C. Please refer to FIG. 3D and FIG. 3E. FIG. 3D shows the X-ray diffraction of the solid base catalyst prepared by fixing the lithium carbonate to alumina molar ratio in FIGS. 3A to 3C and preparing at different calcination temperatures. As a result of the analysis, FIG. 3E is a graph showing the relationship between the transesterification rate of the transesterification reaction of the solid base catalyst in FIG. 3D.
首先,第3D圖中數據由下往上分別是利用煅燒溫度600℃、700℃、800℃、900℃、1000℃所製備之固體鹼觸媒,且碳酸鋰、氧化鋁、不同晶相之鋁酸鋰r-LiAlO2 與t-LiAlO2分別以空心圓、實心圓、空心三角形與實心三角形來標示。當使用煅燒溫度600℃製備固體鹼觸媒時,所偵測到之繞射峰皆屬於起始物氧化鋁及碳酸鋰,因此可以判斷在煅燒溫度為600℃時氧化鋁還沒有獲得足夠的能量來合成鋁酸鋰。當使用煅燒溫度700℃製備固體鹼觸媒時,大部分的繞射峰還是屬於起始物氧化鋁及碳酸鋰,只有少數幾根繞射峰是屬於鋁酸鋰,而此時t-LiAlO2與r-LiAlO2兩種不同晶相的鋁酸鋰均存在於固體鹼觸媒,但是這兩種晶相結構的鋁酸鋰其繞射峰皆不明顯,所以代表結晶性都沒有很好。由以上的因素可以判斷在煅燒溫度為700℃時,雖然已經開始有鋁酸鋰的產生,但此時反應溫度提供的能量還是不夠。當使用煅燒溫度800℃製備固體鹼觸媒時,由圖可知固體鹼觸媒內已經沒有碳酸鋰的存在,且鋁酸鋰之繞射峰也比使用煅燒溫度700℃製備之固體鹼觸媒明顯。另外,t-LiAlO2與r-LiAlO2兩種不同晶相的鋁酸鋰均存在於固體鹼觸媒,故煅燒溫度800℃為製備本發明之固體鹼觸媒較佳的反應溫度。再者,當使用煅燒溫度900℃製備固體鹼觸媒時,僅有為t-LiAlO2晶相結構之鋁酸鋰存在於固體鹼觸媒中,且沒有碳酸鋰殘留,至於少許殘留之氧化鋁可推測為藥品秤取時所造成的誤差。當使用煅燒溫度1000℃製備固體鹼觸媒時,其結果也與煅燒溫度900℃時之結果類似。 First, in the 3D figure, the data from the bottom to the top are solid base catalysts prepared by calcination temperatures of 600 ° C, 700 ° C, 800 ° C, 900 ° C, and 1000 ° C, and lithium carbonate, alumina, and different crystal phases of aluminum. Lithium acid r-LiAlO 2 and t-LiAlO 2 are indicated by hollow circles, filled circles, open triangles and solid triangles, respectively. When a solid base catalyst is prepared using a calcination temperature of 600 ° C, the detected diffraction peaks belong to the starting materials of alumina and lithium carbonate, so it can be judged that the alumina has not obtained sufficient energy at a calcination temperature of 600 ° C. To synthesize lithium aluminate. When using a calcination temperature of 700 ° C to prepare a solid base catalyst, most of the diffraction peaks belong to the starting materials of aluminum oxide and lithium carbonate, and only a few of the diffraction peaks belong to lithium aluminate, and at this time t-LiAlO 2 Lithium aluminate with two different crystal phases of r-LiAlO 2 is present in the solid base catalyst, but the lithium dilithate of these two crystal phases has no diffraction peaks, so the crystallinity is not good. From the above factors, it can be judged that when the calcination temperature is 700 ° C, although the production of lithium aluminate has begun, the energy provided by the reaction temperature is insufficient. When a solid base catalyst is prepared using a calcination temperature of 800 ° C, it can be seen that there is no lithium carbonate in the solid base catalyst, and the diffraction peak of lithium aluminate is also more obvious than the solid base catalyst prepared by using a calcination temperature of 700 ° C. . Further, lithium aluminate having two different crystal phases of t-LiAlO 2 and r-LiAlO 2 is present in the solid base catalyst, so the calcination temperature of 800 ° C is a preferred reaction temperature for preparing the solid base catalyst of the present invention. Furthermore, when a solid base catalyst is prepared using a calcination temperature of 900 ° C, only lithium aluminate which is a t-LiAlO 2 crystal phase structure is present in the solid base catalyst, and no lithium carbonate remains, as for a little residual alumina. It can be presumed to be the error caused by the weighing of the medicine. When a solid base catalyst was prepared using a calcination temperature of 1000 ° C, the results were also similar to those at a calcination temperature of 900 °C.
隨後,將不同煅燒溫度製備之固體鹼觸媒進行轉酯化反應之轉酯率如第3E圖所示,其中固定油醇莫耳比為1:12、固體鹼觸媒用量為6wt%、反應時間為2小時、反 應溫度為65℃。如圖所示,當利用煅燒溫度為600℃及700℃時所製備之固體鹼觸媒在轉酯化反應中時,由於產物還沒生成或是固體鹼觸媒中的鋁酸鋰結晶性不佳,所得到的轉酯率只有29.25%及29.54%。當利用煅燒溫度為800℃及900℃所製備之固體鹼觸媒時,由於生成的鋁酸鋰結晶性佳,轉酯率隨之提高至60.89%及66.59%。然而,當利用煅燒溫度1000℃所製備之固體鹼觸媒時,可能由於溫度太高,所以產生了燒結現象,導致固體鹼觸媒的活性位點減少,使得轉酯率下降至3.80%。 Subsequently, the transesterification rate of the solid base catalyst prepared by different calcination temperatures is shown in FIG. 3E, wherein the fixed oleyl alcohol molar ratio is 1:12, and the solid base catalyst is used in an amount of 6 wt%. Time is 2 hours, anti The temperature should be 65 °C. As shown in the figure, when the solid base catalyst prepared by using the calcination temperature of 600 ° C and 700 ° C is in the transesterification reaction, the product is not formed or the lithium aluminate crystal in the solid base catalyst is not crystalline. Preferably, the transesterification rate obtained is only 29.25% and 29.54%. When the solid base catalyst prepared by calcination temperature of 800 ° C and 900 ° C is used, since the crystallinity of the produced lithium aluminate is good, the transesterification rate is increased to 60.89% and 66.59%. However, when a solid base catalyst prepared by calcination at a temperature of 1000 ° C is used, it may be because the temperature is too high, so that a sintering phenomenon occurs, resulting in a decrease in the active site of the solid base catalyst, so that the transesterification rate is lowered to 3.80%.
最後探討不同煅燒時間對於製備而得之固體鹼觸媒的影響,固定碳酸鋰對氧化鋁之莫耳比為1:1以及煅燒溫度為900℃,煅燒時間則分別以0.5小時、1小時、2小時、3小時、4小時進行。請參考第3F圖與第3G圖,第3F圖係固定第3A圖至第3C中碳酸鋰對氧化鋁莫耳比並以不同煅燒時間所製備之固體鹼觸媒的X射線繞射分析結果,第3G圖係繪示第3F圖之固體鹼觸媒對轉酯化反應的轉酯率關係圖。 Finally, the effects of different calcination time on the solid base catalyst prepared were investigated. The molar ratio of fixed lithium carbonate to alumina was 1:1 and the calcination temperature was 900 °C. The calcination time was 0.5 hour, 1 hour, 2 respectively. Hour, 3 hours, 4 hours. Please refer to FIG. 3F and FIG. 3G. FIG. 3F is a result of X-ray diffraction analysis of the solid base catalyst prepared by fixing the molar ratio of lithium carbonate to alumina in the 3A to 3C and preparing at different calcination times. Fig. 3G is a graph showing the relationship between the transesterification rate of the transesterification reaction of the solid base catalyst in Fig. 3F.
首先,第3F圖中數據由下往上分別是利用煅燒時間0.5小時、1小時、2小時、3小時、4小時所製備之固體鹼觸媒,且氧化鋁與t-LiAlO2分別以實心圓與實心三角形來標示。由圖中可以看到使用不同煅燒時間製備之固體鹼觸媒的圖譜彼此相似,且屬正方晶相結構之鋁酸鋰的吸收峰。然而,使用煅燒時間0.5小時製備之固體鹼觸媒的特徵峰強度與其餘煅燒時間製備之固體鹼觸媒相比較弱,而特徵峰強 度較弱則代表固體鹼觸媒的結晶性較差,故推測煅燒時間0.5小時仍不足以完成反應。 First, the data in the 3F chart is a solid base catalyst prepared by using a calcination time of 0.5 hours, 1 hour, 2 hours, 3 hours, and 4 hours from bottom to top, and alumina and t-LiAlO 2 are respectively solid circles. Mark with a solid triangle. It can be seen from the figure that the spectra of solid base catalysts prepared using different calcination times are similar to each other and belong to the absorption peak of lithium aluminate having a tetragonal phase structure. However, the characteristic peak intensity of the solid base catalyst prepared using the calcination time of 0.5 hours is weaker than that of the solid base catalyst prepared by the remaining calcination time, while the weaker characteristic peak intensity indicates that the solid base catalyst has poor crystallinity, so it is presumed that A calcination time of 0.5 hours is still insufficient to complete the reaction.
隨後,將不同煅燒時間製備之固體鹼觸媒進行轉酯化反應之轉酯率如第3G圖所示,其中固定油醇莫耳比為1:12、固體鹼觸媒用量為6wt%、反應時間為2小時、反應溫度為65℃。如圖所示,當煅燒時間從0.5小時增加到1小時時,轉酯率從37.34%上升至66.59%。然而,當煅燒時間增加至2小時甚至4小時時,轉酯率卻大幅下降,經推測可能的原因是煅燒時間過長導致固體鹼觸媒的形貌發生改變,造成活性位點減少,因此轉酯效果較不理想。 Subsequently, the transesterification rate of the solid base catalyst prepared by different calcination time is shown in FIG. 3G, wherein the fixed oleyl alcohol molar ratio is 1:12, and the solid base catalyst is used in an amount of 6 wt%. The time was 2 hours and the reaction temperature was 65 °C. As shown, when the calcination time was increased from 0.5 hours to 1 hour, the transesterification rate increased from 37.34% to 66.59%. However, when the calcination time is increased to 2 hours or even 4 hours, the transesterification rate is greatly reduced. It is speculated that the reason may be that the calcination time is too long, resulting in a change in the morphology of the solid base catalyst, resulting in a decrease in the active site. The ester effect is less than ideal.
另外,第二固體反應物除了使用市售試藥級之氧化鋁外,亦可利用鋁礬土作為鋁源來進行,且其製備方法如請參考第1圖,在此不再贅述。請參考第4A圖至第4C圖,第4A圖係本發明實驗例1中以鋁礬土作為第二固體反應物時以不同碳酸鋰對鋁礬土莫耳比所製備之固體鹼觸媒對轉酯化反應之轉酯率關係圖,第4B圖係本發明實驗例1中以鋁礬土作為第二固體反應物時以不同煅燒溫度所製備之固體鹼觸媒對轉酯化反應之轉酯率關係圖圖,而第4C圖係本發明實驗例1中以鋁礬土作為第二固體反應物時以不同煅燒時間所製備之固體鹼觸媒對轉酯化反應之轉酯率關係圖。 In addition, the second solid reactant can be carried out by using bauxite as the aluminum source in addition to the alumina of the commercially available reagent grade, and the preparation method thereof is referred to FIG. 1 and will not be described herein. Please refer to FIG. 4A to FIG. 4C. FIG. 4A is a solid base catalyst pair prepared by using lithium bauxite as a second solid reactant in the experimental example 1 of the present invention with different lithium carbonate to bauxite molar ratio. The transesterification ratio diagram of the transesterification reaction, and Fig. 4B shows the transesterification reaction of the solid base catalyst prepared by using different calcination temperatures when the bauxite is used as the second solid reactant in the experimental example 1 of the present invention. The ester rate relationship diagram, and FIG. 4C is a diagram showing the relationship between the transesterification ratio of the solid base catalyst prepared by the different calcination time when the bauxite is used as the second solid reactant in the experimental example 1 of the present invention. .
如第4A圖所示,固定煅燒溫度為800℃以及鍛燒時間為4小時,分別改變碳酸鋰對鋁礬土的莫耳比為1:0.5、1:1、1:2、1:3、1:4製備固體鹼觸媒。當以碳酸鋰與鋁礬土莫耳比為1:4製備固體鹼觸媒時,其轉酯率 可達99.49%。接著,如第4B圖所示,固定碳酸鋰對鋁礬土莫耳比為1:4,改變鍛燒溫度分別為600℃、700℃、800℃、900℃、1000℃製備固體鹼觸媒。當以煅燒溫度為700℃、800℃、900℃、1000℃製備固體鹼觸媒時,其轉酯率均在95%以上,其中以煅燒溫度800℃所製備之固體鹼觸媒的轉酯率更高達99.49%。最後,如第4C圖所示,固定以碳酸鋰對鋁礬土的莫耳比為1:4,且鍛燒溫度為800℃,分別以鍛燒時間1、2、3、4、5小時製備固體鹼觸媒。由圖可知,在以碳酸鋰與鋁礬土製備固體鹼觸媒的製備過中鍛燒時間較佳為3小時。 As shown in Fig. 4A, the fixed calcination temperature is 800 ° C and the calcination time is 4 hours, and the molar ratio of lithium carbonate to bauxite is changed to 1:0.5, 1:1, 1:2, 1:3, respectively. 1:4 Preparation of a solid base catalyst. When a solid base catalyst is prepared by using a molar ratio of lithium carbonate to bauxite of 1:4, the transesterification rate is Up to 99.49%. Next, as shown in FIG. 4B, the molar ratio of lithium carbonate to bauxite was 1:4, and the solid calcination temperature was changed to 600 ° C, 700 ° C, 800 ° C, 900 ° C, and 1000 ° C to prepare a solid alkali catalyst. When the solid base catalyst is prepared at a calcination temperature of 700 ° C, 800 ° C, 900 ° C, and 1000 ° C, the transesterification rate is above 95%, wherein the transesterification rate of the solid base catalyst prepared at a calcination temperature of 800 ° C is used. Up to 99.49%. Finally, as shown in Fig. 4C, the molar ratio of lithium carbonate to bauxite was fixed at 1:4, and the calcination temperature was 800 ° C, and the calcination time was 1, 2, 3, 4, and 5 hours, respectively. Solid base catalyst. As can be seen from the figure, the calcination time in the preparation of the solid base catalyst prepared from lithium carbonate and bauxite is preferably 3 hours.
經由實驗例1之說明可知,本發明不僅可以市售試藥級碳酸鋰與氧化鋁製備出包含鋁酸鋰並具有良好轉酯效果之固體鹼觸媒,更可以利用鋁礬土作為第二固體反應物製備出同樣具有良好轉酯效果之固體鹼觸媒,達到物盡其用之目的。 It can be seen from the description of Experimental Example 1 that the present invention can prepare not only a commercially available reagent grade lithium carbonate and alumina, but also a solid base catalyst containing lithium aluminate and having a good transesterification effect, and bauxite can be used as the second solid. The reactants prepare a solid base catalyst which also has a good transesterification effect, and achieves the best use thereof.
實驗例2係以鋰源作為第一固體反應物並以鈦源作為第二固體反應物,而製得之固體鹼觸媒包含鈦酸鋰。 In Experimental Example 2, a lithium source was used as the first solid reactant and a titanium source was used as the second solid reactant, and the solid base catalyst prepared contained lithium titanate.
在本實驗例中,第一固體反應物係使用碳酸鋰,而第二固體反應物係使用二氧化鈦,且固體鹼觸媒為鈦酸鋰時的製備方法如后。首先,取0.1莫耳二氧化鈦和0.1莫耳的碳酸鋰放入研缽中攪拌均勻。接著,將混合之二氧化鈦與碳酸鋰放入高溫爐以800℃煅燒4個小時後取出研磨成 粉體,即可作為固體鹼觸媒進行後續轉酯化反應。請參考第5A圖至第5F圖,第5A圖與第5B圖係本發明實驗例2中以不同碳酸鋰對二氧化鈦莫耳比所製備之固體鹼觸媒的X射線繞射分析結果及其對轉酯化反應之轉酯率關係圖,第5C圖與第5D圖係固定第5A圖之碳酸鋰對二氧化鈦莫耳比並以不同煅燒溫度所製備之固體鹼觸媒的X射線繞射分析結果及其對轉酯化反應的轉酯率關係圖,第5E圖與第5F圖係固定第5A圖之碳酸鋰對二氧化鈦莫耳比並以不同煅燒時間所製備之固體鹼觸媒的X射線繞射分析結果及其對轉酯化反應的轉酯率關係圖。 In the present experimental example, the first solid reactant used was lithium carbonate, and the second solid reactant was titanium dioxide, and the solid base catalyst was lithium titanate. First, 0.1 mol of titanium dioxide and 0.1 mol of lithium carbonate were placed in a mortar and stirred well. Next, the mixed titanium dioxide and lithium carbonate are placed in a high-temperature furnace and calcined at 800 ° C for 4 hours, and then ground and ground. The powder can be used as a solid base catalyst for subsequent transesterification. Please refer to FIGS. 5A to 5F. FIGS. 5A and 5B are X-ray diffraction analysis results of the solid base catalyst prepared by using different lithium carbonate to titanium dioxide molar ratio in Experimental Example 2 of the present invention and the pair thereof. X-ray diffraction analysis results of the solid base catalyst prepared by different molar calcination temperatures of lithium carbonate to titanium dioxide molar ratio in Figure 5C and Figure 5D. And its transesterification rate diagram for the transesterification reaction, 5E and 5F are X-ray windings of the solid base catalyst prepared by fixing the lithium carbonate molar ratio of the lithium carbonate to the titanium dioxide molar ratio of FIG. 5A and different calcination times. The results of the analytical analysis and its relationship to the transesterification rate of the transesterification reaction.
首先,如第5A圖所示,圖中數據由下往上分別是於製備固體鹼觸媒時碳酸鋰對二氧化鈦的莫耳比為1:1、2:1與3:1,且鈦酸鋰、碳酸鋰與二氧化鈦分別以實心圓、實心正方形與實心三角形來標示。其中,當碳酸鋰與二氧化鈦之莫耳比為1:1與2:1時,鈦酸鋰均存在於固體鹼觸媒。但當碳酸鋰與二氧化鈦之莫耳比為3:1時,可以發現固體鹼觸媒中有殘留之碳酸鋰。此時,將製備而得之固體鹼觸媒進行轉酯化反應。較佳地,反應中係固定其他條件如油醇比1:24、觸媒用量6wt%、反應時間2小時及反應溫度65℃,而固體鹼觸媒之轉酯率如下表3與第5B圖所示。由此可知,以碳酸鋰對二氧化鈦的莫耳比為2:1與3:1製備之包含鈦酸鋰的固體鹼觸媒具有良好的轉酯效果。 First, as shown in Fig. 5A, the data in the figure are from bottom to top, respectively, when the solid base catalyst is prepared, the molar ratio of lithium carbonate to titanium dioxide is 1:1, 2:1 and 3:1, and lithium titanate. Lithium carbonate and titanium dioxide are indicated by solid circles, solid squares and solid triangles, respectively. Wherein, when the molar ratio of lithium carbonate to titanium dioxide is 1:1 and 2:1, lithium titanate is present in the solid base catalyst. However, when the molar ratio of lithium carbonate to titanium dioxide is 3:1, it is found that lithium carbonate remains in the solid base catalyst. At this time, the prepared solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil-to-alcohol ratio of 1:24, a catalyst amount of 6 wt%, a reaction time of 2 hours, and a reaction temperature of 65 ° C are fixed in the reaction, and the transesterification ratio of the solid base catalyst is as shown in Table 3 and Figure 5B. Shown. It can be seen that the solid base catalyst containing lithium titanate prepared by the lithium carbonate to titanium dioxide molar ratio of 2:1 and 3:1 has a good transesterification effect.
接著,固定碳酸鋰對二氧化鈦的莫耳比為2:1且煅燒時間為4小時,並分別以700℃、800℃、900℃、1000℃之煅燒溫度製備固體鹼觸媒。如第5C圖所示,當使用煅燒溫度700℃製備固體鹼觸媒時,所偵測到之繞射峰幾乎都屬於起始物碳酸鋰與二氧化鈦,因此可以判斷在煅燒溫度為700℃時還沒有獲得足夠的能量來合成固體鹼觸媒。當以800℃、900℃、1000℃之煅燒溫度所製備之固體鹼觸媒的圖譜類似,即鈦酸鋰均存在於固體鹼觸媒中。此時,將製備而得之固體鹼觸媒進行轉酯化反應。較佳地,反應中係固定其他條件如油醇比1:24、觸媒用量6wt%、反應時間2小時及反應溫度65℃,而固體鹼觸媒之轉酯率如下表4與第5D圖所示。由此可知,以800℃、900℃、1000℃之煅燒溫度所製備之固體鹼觸媒均可具有平均95%以上之轉酯率。 Next, the molar ratio of the fixed lithium carbonate to the titanium dioxide was 2:1 and the calcination time was 4 hours, and a solid base catalyst was prepared at a calcination temperature of 700 ° C, 800 ° C, 900 ° C, and 1000 ° C, respectively. As shown in Fig. 5C, when a solid base catalyst is prepared using a calcination temperature of 700 ° C, the detected diffraction peaks are almost all of the starting materials of lithium carbonate and titanium dioxide, so it can be judged that the calcination temperature is 700 ° C. Not enough energy is available to synthesize a solid base catalyst. The pattern of the solid base catalyst prepared at a calcination temperature of 800 ° C, 900 ° C, and 1000 ° C is similar, that is, lithium titanate is present in the solid base catalyst. At this time, the prepared solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil-to-alcohol ratio of 1:24, a catalyst amount of 6 wt%, a reaction time of 2 hours, and a reaction temperature of 65 ° C are fixed in the reaction, and the transesterification ratio of the solid base catalyst is as shown in Table 4 and Figure 5D. Shown. From this, it is understood that the solid base catalyst prepared at a calcination temperature of 800 ° C, 900 ° C, and 1000 ° C can have an average transesterification ratio of 95% or more.
最後,如第5E圖所示,固定以碳酸鋰對二氧化鈦的莫耳比為2:1,且鍛燒溫度為800℃,分別以鍛燒時間1、2、3、4小時製備固體鹼觸媒。由圖可知,在以碳酸鋰與二氧化鈦製備固體鹼觸媒的製備過中鍛燒時間較佳為4小時,其餘條件下均見有碳酸鋰之殘留。此時,將製備而得之固體鹼觸媒進行轉酯化反應。較佳地,反應中係固定其他條件如油醇比1:24、觸媒用量6wt%、反應時間2小時及反應溫度65℃,而固體鹼觸媒之轉酯率如下表5與第5F圖所示。由此可知,使用不同煅燒時間製備之固體鹼觸媒的圖譜彼此相似,且在以碳酸鋰與二氧化鈦製備固體鹼觸媒的製備過中鍛燒時間較佳為4小時。 Finally, as shown in Fig. 5E, the molar ratio of lithium carbonate to titanium dioxide is 2:1, and the calcination temperature is 800 ° C, and the solid base catalyst is prepared at 1, 2, 3, and 4 hours respectively. . As can be seen from the figure, the calcination time in the preparation of the solid base catalyst prepared by using lithium carbonate and titanium oxide is preferably 4 hours, and the residue of lithium carbonate is observed under other conditions. At this time, the prepared solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil-to-alcohol ratio of 1:24, a catalyst amount of 6 wt%, a reaction time of 2 hours, and a reaction temperature of 65 ° C are fixed in the reaction, and the transesterification rate of the solid alkali catalyst is as shown in Table 5 and Figure 5F. Shown. From this, it is understood that the patterns of the solid base catalysts prepared using different calcination times are similar to each other, and the calcination time in the preparation of the solid base catalyst prepared from lithium carbonate and titanium oxide is preferably 4 hours.
經由上述說明可知,本發明中第二固體反應物除了可利用鋁源外,以鈦源作為第二固體反應物同樣可以製備出具有良好轉酯效果的固體鹼觸媒。值得說明的是,現今工業界在製備二氧化鈦或是相關製程時往往會產生許多不利於環境的含鈦污泥,利用本發明之方法可期進一步將含鈦的固體廢料回收利用,達到環保之目的。 As can be seen from the above description, in the second solid reactant of the present invention, in addition to the aluminum source, a solid base catalyst having a good transesterification effect can be prepared by using a titanium source as the second solid reactant. It is worth noting that in the current industry, in the preparation of titanium dioxide or related processes, many titanium-containing sludges which are unfavorable to the environment are often produced. The method of the present invention can further recycle the solid waste containing titanium to achieve environmental protection. .
此外,請參考第5G圖,第5G圖係本發明實驗例2中以碳酸鋰與二氧化鈦所製備之固體鹼觸媒之重複使用次數對轉酯率的關係圖。更詳細地說,若能將固體鹼觸媒進行重複使用,則能降低生產生質柴油的成本,提高此固體鹼觸媒的實用價值。據此,在本實驗例中進一步探討包含碳酸鋰之固體鹼觸媒的重複使用次數,並固定轉酯化反應的條件如油醇莫耳比1:24、固體鹼觸媒添加用量6wt%、反應時間4小時、反應溫度65℃。 Further, please refer to Fig. 5G, which is a graph showing the relationship between the number of times of repeated use of the solid base catalyst prepared by lithium carbonate and titanium dioxide in the experimental example 2 of the present invention, and the transesterification ratio. More specifically, if the solid base catalyst can be repeatedly used, the cost of producing the quality diesel can be reduced, and the practical value of the solid base catalyst can be improved. Accordingly, in this experimental example, the number of repeated use of the solid base catalyst containing lithium carbonate is further investigated, and the conditions of the fixed transesterification reaction are as follows: oil alcohol molar ratio 1:24, solid alkali catalyst addition amount 6 wt%, The reaction time was 4 hours and the reaction temperature was 65 °C.
由圖可知,本實驗例之固體鹼觸媒在重複使用10次以前都可得到大於80%的轉酯率,甚至在重複使用第11次時都還有60%的轉酯率,亦即本發明所製備之固體鹼觸媒具有相當之經濟效益。 As can be seen from the figure, the solid base catalyst of this experimental example can obtain a transesterification rate of more than 80% before repeated use for 10 times, and even 60% of the transesterification rate even when the 11th time of repeated use, that is, The solid base catalyst prepared by the invention has considerable economic benefits.
實驗例3係以鈉源或鉀源作為第一固體反應物並以鈦源作為第二固體反應物,而製得之固體鹼觸媒包含鈦酸鈉或鈦酸鉀。 In Experimental Example 3, a sodium source or a potassium source was used as the first solid reactant and a titanium source was used as the second solid reactant, and the solid base catalyst prepared contained sodium titanate or potassium titanate.
在本實驗例中,第一固體反應物係使用碳酸鈉與碳酸鉀,而第二固體反應物係使用二氧化鈦。且固體鹼觸媒的製備係先取1莫耳碳酸鈉或碳酸鉀與1莫耳二氧化鈦混和,以800℃鍛燒4小時後取出研磨成粉體,即可作為固體鹼觸媒。此時,將上述固體鹼觸媒進行轉酯化反應。較佳地,反應中係固定其他條件如油醇比1:36、觸媒用量8wt%、反應時間2小時及反應溫度65℃,而固體鹼觸媒之轉酯率如表6所示。 In this experimental example, the first solid reactant used sodium carbonate and potassium carbonate, and the second solid reactant used titanium dioxide. The solid base catalyst is prepared by first mixing 1 mol of sodium carbonate or potassium carbonate with 1 mol of titanium dioxide, calcining at 800 ° C for 4 hours, and then taking out and grinding into a powder to obtain a solid base catalyst. At this time, the above solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil to alcohol ratio of 1:36, a catalyst amount of 8 wt%, a reaction time of 2 hours, and a reaction temperature of 65 ° C are fixed in the reaction, and the transesterification ratio of the solid base catalyst is shown in Table 6.
經由實驗例3可知,本發明中第一固體反應物除了可利用鋰源外,以鈉源或鉀源作為第一固體反應物同樣可以製備出具有良好轉酯效果的固體鹼觸媒。 It can be seen from Experimental Example 3 that in the present invention, in addition to the lithium source, a solid base catalyst having a good transesterification effect can be prepared by using a sodium source or a potassium source as the first solid reactant.
在本實驗例中,第一固體反應物可為鋰源、鈉源或鉀源,而第二固體反應物為鋯源。此時,可依照下列步驟製得包含鋯酸鋰之固體鹼觸媒。首先,取1莫耳碳酸鋰、碳酸鈉或碳酸鉀與1莫耳二氧化鋯混和,以800℃鍛燒4小時後取出研磨成粉體,即可作為固體鹼觸媒。此時,將上述固體鹼觸媒進行轉酯化反應。較佳地,反應中係固定其他條件如油醇比1:36、觸媒用量8wt%、反應時間2小時及反應溫 度65℃,而固體鹼觸媒之轉酯率如表7所示。藉此得知,本發明中第二固體反應物為鋯源時亦可製備出具有良好轉酯效果的固體鹼觸媒。 In this experimental example, the first solid reactant may be a lithium source, a sodium source or a potassium source, and the second solid reactant is a zirconium source. At this time, a solid base catalyst containing lithium zirconate can be obtained in accordance with the following procedure. First, 1 mol of lithium carbonate, sodium carbonate or potassium carbonate is mixed with 1 mol of zirconia, calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst. At this time, the above solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil to alcohol ratio of 1:36, a catalyst amount of 8 wt%, a reaction time of 2 hours, and a reaction temperature are fixed in the reaction. The degree of transesterification of the solid base catalyst is shown in Table 7. It can be seen that the solid base catalyst having a good transesterification effect can also be prepared when the second solid reactant in the present invention is a zirconium source.
在本實驗例中,第一固體反應物可為鋰源,而第二固體反應物為鉍源。較佳地,第一固體反應物為碳酸鋰,而第二固體反應物為硝酸鉍,此時依照下列步驟製得包含鉍酸鋰之固體鹼觸媒。首先以含浸法混合1莫耳碳酸鋰與2莫耳硝酸鉍,再以800℃鍛燒4小時後取出研磨成粉體,即可作為固體鹼觸媒。然而,在本實驗例中鉍源亦可為氧化鉍,本發明並不欲以此為限。當鉍源為氧化鉍時,係先混合1莫耳碳酸鋰與1莫耳氧化鉍,再以800℃鍛燒4小時後取出研磨成粉體,即完成固體鹼觸媒的製備。 In this experimental example, the first solid reactant may be a lithium source and the second solid reactant is a rhodium source. Preferably, the first solid reactant is lithium carbonate and the second solid reactant is cerium nitrate. At this time, a solid base catalyst comprising lithium niobate is prepared according to the following procedure. First, 1 mol of lithium carbonate and 2 mol of lanthanum nitrate were mixed by an impregnation method, and then calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst. However, in the present experimental example, the ruthenium source may also be ruthenium oxide, and the present invention is not intended to be limited thereto. When the cerium source is cerium oxide, 1 mole of lithium carbonate and 1 mole of cerium oxide are first mixed, and then calcined at 800 ° C for 4 hours, and then ground and ground into powder, that is, the preparation of the solid alkali catalyst is completed.
再者,在本實驗例中第一固體反應物也可以是鈉源或鉀源,且固體鹼觸媒的製備步驟如后。首先混合1莫耳碳酸鈉或碳酸鉀與1莫耳氧化鉍,再以700℃鍛燒4小時後取出研磨成粉體,即為含鉍酸鈉或鉍酸鉀之固體鹼觸媒。 Further, in the present experimental example, the first solid reactant may also be a sodium source or a potassium source, and the preparation procedure of the solid base catalyst is as follows. First, 1 mol of sodium carbonate or potassium carbonate and 1 mol of cerium oxide were mixed, and then calcined at 700 ° C for 4 hours, and then taken out and ground into a powder, which is a solid base catalyst containing sodium citrate or potassium citrate.
接著,利用上述各固體鹼觸媒進行轉酯化反應,且固體鹼觸媒之轉酯率如表8所示。藉此得知,本發明中第二固體反應物為鉍源時亦可製備出具有轉酯效果的固體鹼觸媒,且當第二固體反應物為氧化鉍時所得之固體鹼觸媒的轉酯率較其為硝酸鉍時佳。 Next, the transesterification reaction was carried out by each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 8. It can be seen that, in the present invention, when the second solid reactant is a ruthenium source, a solid base catalyst having a transesterification effect can be prepared, and when the second solid reactant is ruthenium oxide, the solid base catalyst is transferred. The ester ratio is better than when it is cerium nitrate.
在本實驗例中,第一固體反應物可為鋰源,而第二固體反應物為鈮源。較佳地,第一固體反應物為碳酸 鋰,而第二固體反應物為五氧化二鈮。更詳細地說,當碳酸鋰對五氧化二鈮之莫耳比為1:1、2:1與3:1時,可依照下述製備方法分別製備出含偏鈮酸鋰、焦鈮酸鋰與鈮酸鋰之固體鹼觸媒。首先,混合不同莫耳比之碳酸鋰與五氧化二鈮,再以800℃鍛燒4小時後取出研磨成粉體,即可作為固體鹼觸媒。 In this experimental example, the first solid reactant may be a lithium source and the second solid reactant is a rhodium source. Preferably, the first solid reactant is carbonic acid Lithium, and the second solid reactant is antimony pentoxide. In more detail, when the molar ratio of lithium carbonate to antimony pentoxide is 1:1, 2:1 and 3:1, lithium bismuth niobate and lithium pyroantimonate may be separately prepared according to the following preparation methods. Solid base catalyst with lithium niobate. First, lithium carbonate and antimony pentoxide of different molar ratios are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst.
另外,在本實驗例中,第一固體反應物亦可為鈉源或鉀源。較佳地,第一固體反應物為碳酸鈉或碳酸鉀,且其製備固體鹼觸媒的方法與以碳酸鋰製備固體鹼觸媒相同,在此不再贅述。 Further, in the present experimental example, the first solid reactant may also be a sodium source or a potassium source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the method for preparing the solid base catalyst is the same as the preparation of the solid base catalyst with lithium carbonate, and details are not described herein again.
接著,利用上述各固體鹼觸媒進行轉酯化反應,且固體鹼觸媒之轉酯率如表9所示。由此可知,本發明中第二固體反應物為鈮源時亦可製備出具有轉酯效果的固體鹼觸媒,亦即日後可回收含鈮廢料而以固體鹼觸媒的方式再生利用於製作生質柴油,達到物盡其用之功效。 Next, the transesterification reaction was carried out by each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 9. Therefore, in the present invention, when the second solid reactant is a ruthenium source, a solid base catalyst having a transesterification effect can be prepared, that is, a ruthenium-containing waste can be recovered in the future and recycled by a solid alkali catalyst. Biodiesel is used to achieve the best results.
在本實驗例中,第一固體反應物可為鋰源或鈉源,而第二固體反應物為釩源。其中當第一固體反應物為碳酸鈉以及第二固體反應物為釩酸銨時,可以碳酸鈉對釩酸銨之莫耳比為3:1或1:1,並依照下述製備方法分別製備出含正釩酸鈉或偏釩酸鈉之固體鹼觸媒。更詳細地來說,先混合不同莫耳比之碳酸鈉與釩酸銨,再以800℃鍛燒4小時後取出研磨成粉體,即可作為含正釩酸鈉或偏釩酸鈉之固體鹼觸媒。而正釩酸鋰的製備方法大致如前文所述,在此不再贅述。 In this experimental example, the first solid reactant may be a lithium source or a sodium source, and the second solid reactant is a vanadium source. Wherein when the first solid reactant is sodium carbonate and the second solid reactant is ammonium vanadate, the molar ratio of sodium carbonate to ammonium vanadate is 3:1 or 1:1, and is separately prepared according to the following preparation method. A solid base catalyst containing sodium orthovanadate or sodium metavanadate. In more detail, sodium carbonate and ammonium vanadate are mixed with different molar ratios, and then calcined at 800 ° C for 4 hours, and then ground and ground into powder, which can be used as a solid containing sodium orthovanadate or sodium metavanadate. Alkali catalyst. The preparation method of lithium orthovanadate is substantially as described above, and will not be described herein.
接著,利用上述各固體鹼觸媒進行轉酯化反應,且固體鹼觸媒之轉酯率如表10所示。藉此得知,本發明中第二固體反應物為釩源時亦可製備出具有轉酯效果的固體鹼觸媒,亦即日後可回收含釩廢料而以固體鹼觸媒的方式再生利用於製作生質柴油,達到物盡其用之功效。 Next, the transesterification reaction was carried out by using each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 10. It can be seen that in the present invention, when the second solid reactant is a vanadium source, a solid alkali catalyst having a transesterification effect can be prepared, that is, a vanadium-containing waste can be recovered in the future and recycled by a solid alkali catalyst. Produce biodiesel to achieve the best results.
在本實驗例中,第一固體反應物可為鈉源或鉀源,而第二固體反應物為鐵源。較佳地,第一固體反應物為碳酸鈉或碳酸鉀,而第二固體反應物為氧化鐵,且可依照下述製備方法分別製備出含鐵酸鈉、鐵酸鉀、過氧鐵酸鈉或過氧鐵酸鉀之固體鹼觸媒。首先,混合1或3莫耳碳酸鈉或碳酸鉀與1莫耳氧化鐵,再以800℃鍛燒4小時後取出研磨成粉體,即可作為固體鹼觸媒。接著,利用上述固體鹼觸媒進行轉酯化反應,且固體鹼觸媒之轉酯率如表11所示。藉此得知,本發明中第二固體反應物為鐵源時亦可製備出具有良好轉酯效果的固體鹼觸媒。 In this experimental example, the first solid reactant may be a sodium source or a potassium source, and the second solid reactant is an iron source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the second solid reactant is iron oxide, and the sodium ferrite-containing, potassium ferrite, and sodium peroxyferrate can be respectively prepared according to the following preparation methods. Or a solid base catalyst of potassium peroxate. First, 1 or 3 mol of sodium carbonate or potassium carbonate and 1 mol of iron oxide are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst. Next, the transesterification reaction was carried out by the above solid base catalyst, and the transesterification ratio of the solid base catalyst was as shown in Table 11. From this, it is known that the solid base catalyst having a good transesterification effect can also be prepared when the second solid reactant in the present invention is an iron source.
在本實驗例中,第一固體反應物可為鋰源、鈉源或鉀源,而第二固體反應物為硼源。較佳地,第一固體反應物為碳酸鈉或碳酸鉀,而第二固體反應物為氧化硼,且可依照下述製備方法分別製備出含硼酸鈉或硼酸鉀之固體鹼 觸媒。首先,混合2莫耳碳酸鋰、碳酸鈉或碳酸鉀與1莫耳氧化硼,再以800℃鍛燒4小時後取出研磨成粉體,即可作為固體鹼觸媒。接著,利用上述固體鹼觸媒進行轉酯化反應,且固體鹼觸媒之轉酯率如表12所示。藉此得知,本發明中第二固體反應物為硼源時亦可製備出具有轉酯效果的固體鹼觸媒,亦即日後可回收含硼廢料而以固體鹼觸媒的方式再生利用於製作生質柴油,達到物盡其用之功效。 In this experimental example, the first solid reactant may be a lithium source, a sodium source or a potassium source, and the second solid reactant is a boron source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the second solid reactant is boron oxide, and the solid base containing sodium borate or potassium borate can be separately prepared according to the following preparation method. catalyst. First, 2 mol of lithium carbonate, sodium carbonate or potassium carbonate and 1 mol of boron oxide are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst. Next, the transesterification reaction was carried out by the above solid base catalyst, and the transesterification ratio of the solid base catalyst was as shown in Table 12. Therefore, in the present invention, when the second solid reactant is a boron source, a solid base catalyst having a transesterification effect can be prepared, that is, a boron-containing waste can be recovered in the future and recycled by a solid alkali catalyst. Produce biodiesel to achieve the best results.
在本實驗例中,第一固體反應物為鋰源,而第二固體反應物為鎢源。較佳地,第一固體反應物為碳酸鋰,而第二固體反應物為氧化鎢。更詳細地說,當碳酸鋰對氧化鎢之莫耳比為3:1與1:1時,可依照下述製備方法分別製備出含過氧鎢酸鋰與鎢酸鋰之固體鹼觸媒。首先,混合不同莫耳比之碳酸鋰與氧化鎢,再以800℃鍛燒4小時後取出研磨成粉體,即可作為固體鹼觸媒。 In this experimental example, the first solid reactant is a lithium source and the second solid reactant is a tungsten source. Preferably, the first solid reactant is lithium carbonate and the second solid reactant is tungsten oxide. In more detail, when the molar ratio of lithium carbonate to tungsten oxide is 3:1 and 1:1, a solid base catalyst containing lithium peroxytungstate and lithium tungstate can be separately prepared according to the following preparation method. First, lithium carbonate and tungsten oxide of different molar ratios are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst.
另外,在本實驗例中,第一固體反應物亦可為鈉源或鉀源。較佳地,第一固體反應物為碳酸鈉或碳酸鉀,且其製備固體鹼觸媒的方法與以碳酸鋰製備固體鹼觸媒相同,在此不再贅述。 Further, in the present experimental example, the first solid reactant may also be a sodium source or a potassium source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the method for preparing the solid base catalyst is the same as the preparation of the solid base catalyst with lithium carbonate, and details are not described herein again.
接著,利用上述各固體鹼觸媒進行轉酯化反應,且固體鹼觸媒之轉酯率如表13所示。藉此得知,本發明中第二固體反應物為鎢源時亦可製備出具有良好轉酯效果的固體鹼觸媒。 Next, the transesterification reaction was carried out by using each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 13. It can be seen from the above that in the present invention, a solid base catalyst having a good transesterification effect can also be prepared when the second solid reactant is a tungsten source.
在本實驗例中,第一固體反應物為鋰源,而第二固體反應物為鉬源。較佳地,第一固體反應物為碳酸鋰,而第二固體反應物為三氧化鉬。更詳細地說,當碳酸鋰對三氧化鉬之莫耳比為3:1與1:1時,可依照下述製備方法分別製備出含過氧鉬酸鋰與鉬酸鋰之固體鹼觸媒。首先,混合不同莫耳比之碳酸鋰與氧化鎢,再以800℃鍛燒4小時後取出研磨成粉體,即可作為固體鹼觸媒。 In this experimental example, the first solid reactant is a lithium source and the second solid reactant is a molybdenum source. Preferably, the first solid reactant is lithium carbonate and the second solid reactant is molybdenum trioxide. In more detail, when the molar ratio of lithium carbonate to molybdenum trioxide is 3:1 and 1:1, a solid base catalyst containing lithium peroxodimolybdate and lithium molybdate can be separately prepared according to the following preparation method. . First, lithium carbonate and tungsten oxide of different molar ratios are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst.
另外,在本實驗例中,第一固體反應物亦可為鈉源或鉀源。較佳地,第一固體反應物為碳酸鈉或碳酸鉀,且其製備固體鹼觸媒的方法與以碳酸鋰製備固體鹼觸媒相同,在此不再贅述。 Further, in the present experimental example, the first solid reactant may also be a sodium source or a potassium source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the method for preparing the solid base catalyst is the same as the preparation of the solid base catalyst with lithium carbonate, and details are not described herein again.
接著,利用上述各固體鹼觸媒進行轉酯化反應,且固體鹼觸媒之轉酯率如表14所示。藉此得知,本發明中第二固體反應物為鉬源時亦可製備出具有良好轉酯效果的固體鹼觸媒。 Next, the transesterification reaction was carried out by using each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 14. From this, it is known that the solid base catalyst having a good transesterification effect can also be prepared when the second solid reactant in the present invention is a molybdenum source.
在實驗例12至17中,第一固體反應物可為鋰源、鈉源或鉀源,而第二固體反應物則分別為鈷源(實驗例12)、鉻源(實驗例13)、錳源(實驗例14)、鎳源(實驗例15)、銅源(實驗例16)以及鋅源(實驗例17)。具體而言,第一固體反應物為碳酸鋰,而第二固體反應物可為如氧化鉻、二氧化錳、氧化鈷、氧化鎳、氧化銅以及氧化鋅。至於製備固體鹼觸媒的方法大致與實驗例1至實驗例11相同,在此不再贅述。 In Experimental Examples 12 to 17, the first solid reactant may be a lithium source, a sodium source or a potassium source, and the second solid reactant is a cobalt source (Experimental Example 12), a chromium source (Experimental Example 13), and manganese. Source (Experimental Example 14), nickel source (Experimental Example 15), copper source (Experimental Example 16), and zinc source (Experimental Example 17). Specifically, the first solid reactant is lithium carbonate, and the second solid reactant may be, for example, chromium oxide, manganese dioxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide. The method for preparing the solid base catalyst is substantially the same as that of Experimental Example 1 to Experimental Example 11, and will not be described herein.
接著,利用上述各固體鹼觸媒進行轉酯化反應之轉酯率如表15所示,可知本發明中第二固體反應物為鈷源、鉻源、錳源、鎳源、銅源以及鋅源時亦可製備出具有轉酯效果的固體鹼觸媒,亦即日後可回收含有上述金屬的廢料 而以固體鹼觸媒的方式再生利用於製作生質柴油,達到物盡其用之功效。 Next, the transesterification ratio of the transesterification reaction by each of the above solid base catalysts is shown in Table 15, and it is understood that the second solid reactant in the present invention is a cobalt source, a chromium source, a manganese source, a nickel source, a copper source, and zinc. A solid base catalyst having a transesterification effect can also be prepared at the source, that is, a waste containing the above metal can be recovered in the future. It is recycled by solid alkali catalyst to produce biodiesel, which can achieve the best effect.
在比較例1中係以習知氧化鈣(購自片山試藥股份有限公司,台灣)為固體鹼觸媒。如前文所述,氧化鈣為目前常見用於製造生質柴油的固體鹼觸媒,但氧化鈣的空氣穩定度差,易吸收空氣中的水份與二氧化碳而失效。將比較例1之氧化鈣、本發明中實驗例1與實驗例2三種固體鹼觸媒暴露於恆溫25℃、相對溼度50%的空間中,並分別在靜置0小時、24小時、48小時、72小時後進行轉酯化反應。較佳地,轉酯化反應之條件分別為油醇莫耳比1:24、固體鹼觸 媒添加用量6wt%、反應時間2小時與反應溫度65℃,而三種固體鹼觸媒對油品之轉酯率均已列於表16中。具體而言,前述所採用之油品為大豆油(購自長城企業股份有限公司),然本發明並不欲以此為限。 In Comparative Example 1, a conventional calcium oxide (purchased from Katayama Pharmaceutical Co., Ltd., Taiwan) was used as a solid base catalyst. As mentioned above, calcium oxide is a solid base catalyst commonly used in the manufacture of biodiesel, but calcium oxide has poor air stability and easily absorbs moisture and carbon dioxide in the air and fails. The calcium oxide of Comparative Example 1 and the three solid base catalysts of Experimental Example 1 and Experimental Example 2 of the present invention were exposed to a space at a constant temperature of 25 ° C and a relative humidity of 50%, and were allowed to stand for 0 hours, 24 hours, and 48 hours, respectively. After 72 hours, the transesterification reaction was carried out. Preferably, the conditions of the transesterification reaction are oleyl alcohol molar ratio 1:24, solid alkali contact The amount of the medium added was 6 wt%, the reaction time was 2 hours, and the reaction temperature was 65 ° C, and the transesterification rates of the three solid base catalysts for the oil were listed in Table 16. Specifically, the oil product used in the foregoing is soybean oil (purchased from Great Wall Enterprise Co., Ltd.), but the present invention is not intended to be limited thereto.
由表16可知,鋁酸鋰在暴露於空氣中24小時後,轉酯率就由原本的98.06%下降為74.97%,在暴露於空氣中48小時及72小時後,鋁酸鋰的轉酯率又下降至57.65%及51.92%。而鈦酸鋰在暴露於空氣中24小時、48小時與72小時後,其轉酯率僅從99.28%些微下降至90.17%。反觀氧化鈣在暴露於空氣中24小時後便已經從原本的96.66%大幅下降至3.00%,故可知雖然固體鹼觸媒在暴露於空氣中後都會使得其轉酯率降低,但本發明所提供之固體鹼觸媒,如鋁酸鋰與鈦酸鋰,除了對油品的轉酯效果較氧化鈣好以外,相對地也較氧化鈣穩定。 It can be seen from Table 16 that after exposure to air for 24 hours, the transesterification rate of lithium aluminate decreased from 98.06% to 74.97%, and the transesterification rate of lithium aluminate after 48 hours and 72 hours of exposure to air. It dropped to 57.65% and 51.92%. When the lithium titanate was exposed to air for 24 hours, 48 hours and 72 hours, the transesterification rate decreased only slightly from 99.28% to 90.17%. In contrast, calcium oxide has been greatly reduced from the original 96.66% to 3.00% after exposure to air for 24 hours, so it is known that although the solid base catalyst reduces its transesterification rate after exposure to air, the present invention provides The solid base catalysts, such as lithium aluminate and lithium titanate, are relatively stable compared to calcium oxide, except that the transesterification effect on the oil is better than that of calcium oxide.
在比較例2中,固體鹼觸媒係藉由先混合1莫耳碳酸鈣(CaCO3)與1莫耳二氧化鈦後再以800℃鍛燒4小時製備而成。 In Comparative Example 2, the solid base catalyst was prepared by first mixing 1 mol of calcium carbonate (CaCO 3 ) with 1 mol of titanium dioxide and then calcining at 800 ° C for 4 hours.
在比較例3中,固體鹼觸媒係藉由先混合1莫耳氫氧化鎂(Mg(OH)2)與1莫耳二氧化鋯後再以800℃鍛燒4小時製備而成。 In Comparative Example 3, the solid base catalyst was prepared by first mixing 1 mol of magnesium hydroxide (Mg(OH) 2 ) with 1 mol of zirconium dioxide and then calcining at 800 ° C for 4 hours.
在比較例4中,固體鹼觸媒係藉由先混合1莫耳氫氧化鎂、1莫耳碳酸鈣、1莫耳無水醋酸鍶(Sr(CH3COO)2)或1莫耳無水醋酸鋇(Ba(CH3COO)2)與1莫耳氧化鉍後再以700℃至800℃鍛燒4小時製備而成。 In Comparative Example 4, the solid base catalyst was first mixed with 1 mole of magnesium hydroxide, 1 mole of calcium carbonate, 1 mole of anhydrous cesium acetate (Sr(CH 3 COO) 2 ) or 1 mole of anhydrous cesium acetate. (Ba(CH 3 COO) 2) and 1 mole of cerium oxide are then calcined at 700 ° C to 800 ° C for 4 hours.
在比較例5中,固體鹼觸媒係藉由先混合3莫耳氫氧化鎂或碳酸鈣與1莫耳五氧化二鈮後再以800℃鍛燒4小時製備而成。 In Comparative Example 5, the solid base catalyst was prepared by first mixing 3 mol of magnesium hydroxide or calcium carbonate with 1 mol of bismuth pentoxide and then calcining at 800 ° C for 4 hours.
在比較例6中,固體鹼觸媒係藉由先混合1莫耳氫氧化鎂、碳酸鈣或碳酸鍶(SrCO3)與1莫耳氧化鎢後再以800℃鍛燒4小時製備而成。 In Comparative Example 6, the solid base catalyst was prepared by first mixing 1 mol of magnesium hydroxide, calcium carbonate or strontium carbonate (SrCO 3 ) with 1 mol of tungsten oxide and then calcining at 800 ° C for 4 hours.
在比較例7中,固體鹼觸媒係藉由先混合1莫耳氫氧化鎂、碳酸鈣或碳酸鍶與1莫耳三氧化鉬後再以800℃鍛燒4小時製備而成。 In Comparative Example 7, the solid base catalyst was prepared by first mixing 1 mol of magnesium hydroxide, calcium carbonate or cesium carbonate with 1 mol of molybdenum trioxide and then calcining at 800 ° C for 4 hours.
在比較例8中,固體鹼觸媒係藉由先混合1莫耳碳酸鈣與1莫耳氧化硼後再以800℃鍛燒4小時製備而成。 In Comparative Example 8, the solid base catalyst was prepared by first mixing 1 mol of calcium carbonate with 1 mol of boron oxide and then calcining at 800 ° C for 4 hours.
在比較例9中,固體鹼觸媒係藉由先混合1莫耳氫氧化鎂與1莫耳二氧化鋯後再以800℃鍛燒4小時製備而成。 In Comparative Example 9, the solid base catalyst was prepared by first mixing 1 mol of magnesium hydroxide with 1 mol of zirconium dioxide and then calcining at 800 ° C for 4 hours.
使用上述實驗例2、實驗例3、實驗例4、實驗例5、實驗例6、實驗例9、實驗例10、實驗例11與比較例2至比較例9所製備之固體鹼觸媒進行轉酯化反應後,比較其轉酯率如表17所示。必須說明的是,此處各實驗例中均採最佳化條件製備固體鹼觸媒,但本發明並不欲以此為限。 The solid base catalyst prepared in the above Experimental Example 2, Experimental Example 3, Experimental Example 4, Experimental Example 5, Experimental Example 6, Experimental Example 9, Experimental Example 10, Experimental Example 11 and Comparative Example 2 to Comparative Example 9 was used for the conversion. After the esterification reaction, the transesterification ratio was as shown in Table 17. It should be noted that the solid base catalyst is prepared under optimized conditions in each of the experimental examples, but the present invention is not intended to be limited thereto.
由表17可知,本發明以如鋰、鈉、鉀等鹼金族元素作為第一固體反應物所製備之固體鹼觸媒在轉酯化反 應上的表現較以如鎂、鈣、鍶或鋇等鹼土族元素作為第一固體反應物所製備之固體鹼觸媒優異。 It can be seen from Table 17 that the solid base catalyst prepared by using the alkali gold group element such as lithium, sodium or potassium as the first solid reactant is in the transesterification reaction. The performance is superior to a solid base catalyst prepared by using an alkaline earth element such as magnesium, calcium, barium or strontium as the first solid reactant.
綜上所述,本發明所提供之用以製造生質柴油的固體鹼觸媒對於油品具有良好的轉酯效果,且較習知固體鹼觸媒穩定並可重複回收利用,可有效降低製造生質柴油的成本。另外,由於本發明中用以製備固體鹼觸媒之第二固體反應物係可取材自生活或產業中常見之固體廢料,進一步以使得地球有限的資源能夠物盡其用,同時亦符合現今環保標準。 In summary, the solid base catalyst for producing biodiesel provided by the present invention has good transesterification effect on oil, and is stable and recyclable than conventional solid base catalyst, and can effectively reduce manufacturing. The cost of biodiesel. In addition, since the second solid reactant used in the preparation of the solid alkali catalyst in the present invention can be obtained from solid waste which is common in life or industry, further enables the limited resources of the earth to be utilized as much as possible, and is also in line with the current environmental protection. standard.
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.
S100、S102、S104‧‧‧步驟 S100, S102, S104‧‧‧ steps
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