TWI755128B - Method for synthesizing propylene glycol methyl ether - Google Patents
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本發明係關於一種觸媒的製備方法，尤其是一種複合式固體鹼觸媒的製備方法、其製備之複合式固體鹼觸媒及丙二醇甲醚的合成方法。 The invention relates to a preparation method of a catalyst, in particular to a preparation method of a composite solid base catalyst, a composite solid base catalyst prepared by the catalyst and a synthesis method of propylene glycol methyl ether.
醇醚是許多化學產品的組成成分，可作為各類的消費產品和工業應用，其中丙二醇甲醚(PM)可用於化工、農業、汽車、油漆、清漆工業，其商業生產方法係藉由環氧丙烷(PO)與甲醇在催化劑的存在下催化生成。 Glycol ethers are constituents of many chemical products and can be used as a variety of consumer products and industrial applications. Among them, propylene glycol methyl ether (PM) can be used in the chemical, agricultural, automotive, paint and varnish industries. Its commercial production method is by epoxy resin. Propane (PO) and methanol are catalytically generated in the presence of a catalyst.
一般來說，環氧化物的開環反應會產生異構體，以丙二醇甲醚舉例，其具有α-異構體(1-甲氧基-2-丙醇)和β-異構體(2-甲氧基-1-丙醇)，兩者在應用與毒性之間均有差異，例如α-異構體的毒性低於β-異構體，故需要具有一種高選擇性的觸媒。 In general, the ring-opening reaction of epoxides produces isomers, exemplified by propylene glycol methyl ether, which has both the α-isomer (1-methoxy-2-propanol) and the β-isomer (2 -Methoxy-1-propanol), both of which have differences in application and toxicity. For example, the toxicity of α-isomer is lower than that of β-isomer, so a catalyst with high selectivity is required.
傳統常用的催化劑為甲醇鈉和氫氧化鈉等勻相催化劑，其顯示出具有高活性及高選擇性之特性，然而，這類觸媒在產物中會有金屬殘留量、產生廢液及需額外之分 離成本等等問題。與之相比，現今研究發現，固體鹼觸媒可克服勻相催化劑的缺點，故為一重要的發展方向。 The traditional commonly used catalysts are homogeneous catalysts such as sodium methoxide and sodium hydroxide, which show the characteristics of high activity and high selectivity. However, such catalysts will have metal residues in the product, generate waste liquid and require additional difference cost, etc. In contrast, current studies have found that solid base catalysts can overcome the shortcomings of homogeneous catalysts, so it is an important development direction.
有鑑於此，如何開發出一種可取代勻相觸媒的固體鹼觸媒，並調控其配方以提升觸媒材料的催化活性、穩定性及選擇性，遂成相關業者努力的目標。 In view of this, how to develop a solid base catalyst that can replace the homogeneous catalyst, and how to adjust its formula to improve the catalytic activity, stability and selectivity of the catalyst material, has become the goal of the relevant industry.
本發明之一目的是在於提供一種複合式固體鹼觸媒的製備方法、其製備之複合式固體鹼觸媒及丙二醇甲醚的合成方法，藉由共沉澱法製備MgO-Al2O3複合式固體鹼觸媒，並調整鎂鋁的莫耳比以及鍛燒溫度，以得到最適化功能性之觸媒，並且運用於催化甲醇與環氧丙烷以合成丙二醇甲醚。 One object of the present invention is to provide a method for preparing a composite solid base catalyst, a method for synthesizing the composite solid base catalyst prepared by the catalyst and propylene glycol methyl ether, and preparing the MgO-Al 2 O 3 composite formula by coprecipitation It is a solid base catalyst, and the molar ratio of magnesium and aluminum and the calcination temperature are adjusted to obtain the catalyst with optimized functionality, and it is used to catalyze methanol and propylene oxide to synthesize propylene glycol methyl ether.
本發明之一實施方式係在於提供一種複合式固體鹼觸媒的製備方法，包含進行一溶液準備步驟、進行一滴定步驟、進行一熟化步驟以及進行一鍛燒步驟。溶液準備步驟係將一催化活性成分前驅物作為一前驅物溶液，其中前驅物溶液含有一鎂離子以及一鋁離子，滴定步驟係將前驅物溶液以一逆向滴定的方式滴入一氨水溶液中，並均勻攪拌形成一觸媒母液，熟化步驟係將觸媒母液進行熟化以形成一觸媒前驅物，鍛燒步驟係將觸媒前驅物於一流動空氣下鍛燒，以得到一複合式固體鹼觸媒。 One embodiment of the present invention is to provide a method for preparing a composite solid base catalyst, which includes a solution preparation step, a titration step, a maturation step, and a calcination step. The solution preparation step is to use a catalytically active component precursor as a precursor solution, wherein the precursor solution contains a magnesium ion and an aluminum ion, and the titration step is to drop the precursor solution into an ammonia solution in a reverse titration manner, And uniformly stir to form a catalyst mother liquor, the curing step is to ripen the catalyst mother liquor to form a catalyst precursor, and the calcination step is to calcine the catalyst precursor under a flowing air to obtain a composite solid base catalyst.
依據前述實施方式之複合式固體鹼觸媒的製備方法，其中催化活性成分前驅物可為硝酸鎂與硝酸鋁之混合 液。 According to the preparation method of the composite solid base catalyst of the foregoing embodiment, the catalytic active component precursor can be a mixture of magnesium nitrate and aluminum nitrate liquid.
依據前述實施方式之複合式固體鹼觸媒的製備方法，其中於前驅物溶液中，鎂離子與鋁離子的莫耳比可為2至10。 According to the preparation method of the composite solid base catalyst according to the foregoing embodiment, in the precursor solution, the molar ratio of magnesium ions to aluminum ions can be 2 to 10.
依據前述實施方式之複合式固體鹼觸媒的製備方法，其中前驅物溶液的滴定速率可為0.5滴/秒。 According to the preparation method of the composite solid base catalyst according to the foregoing embodiment, the titration rate of the precursor solution may be 0.5 drops/second.
依據前述實施方式之複合式固體鹼觸媒的製備方法，其中觸媒母液之pH值可大於或等於10。 According to the preparation method of the composite solid base catalyst according to the foregoing embodiment, the pH value of the catalyst mother liquor can be greater than or equal to 10.
依據前述實施方式之複合式固體鹼觸媒的製備方法，其中熟化步驟之時間可為10小時至12小時。 According to the preparation method of the composite solid base catalyst according to the foregoing embodiment, the time of the aging step may be 10 hours to 12 hours.
依據前述實施方式之複合式固體鹼觸媒的製備方法，其中於熟化步驟後及鍛燒步驟前更包含進行一純化步驟以及進行一乾燥步驟。純化步驟係將觸媒前驅物進行真空過濾除水後，並以去離子水進行清洗，而乾燥步驟係將純化後之觸媒前驅物放置於烘箱中乾燥過夜。 According to the preparation method of the composite solid base catalyst according to the above-mentioned embodiment, after the aging step and before the calcining step, a purification step and a drying step are further included. In the purification step, the catalyst precursor is subjected to vacuum filtration to remove water, and then washed with deionized water. In the drying step, the purified catalyst precursor is placed in an oven to dry overnight.
依據前述實施方式之複合式固體鹼觸媒的製備方法，其中鍛燒步驟之溫度可為500℃至600℃。 According to the preparation method of the composite solid base catalyst according to the foregoing embodiment, the temperature of the calcination step may be 500°C to 600°C.
本發明之另一實施方式係在於提供一種複合式固體鹼觸媒，所述複合式固體鹼觸媒為由前述製備方法製備而得。 Another embodiment of the present invention is to provide a composite solid base catalyst prepared by the aforementioned preparation method.
本發明之又一實施方式係在於提供一種丙二醇甲醚的合成方法，其包含下列步驟。首先，提供一種複合式固體鹼觸媒，所述複合式固體鹼觸媒為由前述製備方法製備而得。接著，進行一開環醚化反應，其係於一反應器中， 以所述複合式固體鹼觸媒作為催化劑，將甲醇與環氧丙烷進行開環醚化反應，以得到丙二醇甲醚。 Another embodiment of the present invention is to provide a method for synthesizing propylene glycol methyl ether, which comprises the following steps. First, a composite solid base catalyst is provided, and the composite solid base catalyst is prepared by the aforementioned preparation method. Next, carry out a ring-opening etherification reaction, which is in a reactor, Using the composite solid base catalyst as a catalyst, methanol and propylene oxide are subjected to a ring-opening etherification reaction to obtain propylene glycol methyl ether.
依據前述實施方式之丙二醇甲醚的合成方法，其中反應器可為連續式高壓固定床反應器或高溫高壓反應釜式批次反應器。 According to the synthesis method of propylene glycol methyl ether according to the foregoing embodiment, the reactor can be a continuous high pressure fixed bed reactor or a high temperature and high pressure reactor type batch reactor.
藉此，本發明利用共沉澱法製備MgO-Al2O3複合式固體鹼觸媒，並調整鎂鋁莫耳比例來優化觸媒配方，所製備之觸媒可用於催化開環醚化反應以合成丙二醇甲醚，可達到高轉化率及高選擇率。 Thereby, the present invention utilizes the co-precipitation method to prepare the MgO-Al 2 O 3 composite solid base catalyst, and adjusts the magnesium-aluminum molar ratio to optimize the catalyst formula, and the prepared catalyst can be used to catalyze the ring-opening etherification reaction to Synthesis of propylene glycol methyl ether can achieve high conversion and high selectivity.
100:複合式固體鹼觸媒的製備方法 100: the preparation method of composite solid alkali catalyst
110,120,130,140:步驟 110, 120, 130, 140: Steps
200:丙二醇甲醚的合成方法 200: the synthetic method of propylene glycol methyl ether
210,220:步驟 210, 220: Steps
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下：第1圖係繪示本發明之一實施方式之一種複合式固體鹼觸媒的製備方法的步驟流程圖；第2圖係繪示本發明之另一實施方式之丙二醇甲醚的合成方法的步驟流程圖；第3A圖係繪示實施例1至實施例5以及比較例1的孔徑分布圖；第3B圖係繪示實施例6至實施例9以及比較例2的孔徑分布圖；第4A圖係繪示實施例1至實施例5以及比較例1的XRD繞射分析圖；第4B圖係繪示實施例6至實施例9的XRD繞射分析圖； 第5A圖係繪示實施例1、實施例2、實施例4、實施例5以及比較例1的程溫脫附反應分析圖；第5B圖係繪示實施例6至實施例9以及比較例2至比較例3的程溫脫附反應分析圖；第6A圖係繪示實施例2的FESEM表面形貌；第6B圖係繪示實施例2的EDS能量分散光譜圖；第7圖係繪示實施例1至實施例5的環氧丙烷轉化率與丙二醇甲醚選擇率的曲線圖；第8圖係繪示不同壓錠強度之觸媒的環氧丙烷轉化率與丙二醇甲醚的曲線圖；以及第9圖係繪示實施例2於不同反應時間下的環氧丙烷轉化率與丙二醇甲醚選擇率的曲線圖。 In order to make the above-mentioned and other objects, features, advantages and embodiments of the present invention more clearly understood, the accompanying drawings are described as follows: Fig. 1 shows a composite solid base catalyst according to an embodiment of the present invention. Figure 2 shows a flow chart of the steps of the synthesis method of propylene glycol methyl ether according to another embodiment of the present invention; Figure 3A shows Example 1 to Example 5 and Comparative Example 1 Figure 3B shows the pore size distribution of Examples 6 to 9 and Comparative Example 2; Figure 4A shows the XRD diffraction analysis of Examples 1 to 5 and Comparative Example 1 ; Figure 4B depicts the XRD diffraction analysis diagram of Example 6 to Example 9; Fig. 5A shows the analysis diagram of the temperature range desorption reaction of Example 1, Example 2, Example 4, Example 5 and Comparative Example 1; Fig. 5B shows Example 6 to Example 9 and Comparative Example 2 to Comparative Example 3, the desorption reaction analysis diagram of the process temperature; Figure 6A depicts the FESEM surface morphology of Example 2; Figure 6B depicts the EDS energy dispersion spectrum of Example 2; Figure 7 depicts A graph showing the propylene oxide conversion rate and propylene glycol methyl ether selectivity of Examples 1 to 5; Figure 8 is a graph showing the propylene oxide conversion rate and propylene glycol methyl ether of catalysts with different tablet strengths; And FIG. 9 is a graph showing the conversion rate of propylene oxide and the selectivity of propylene glycol methyl ether under different reaction times of Example 2.
下述將更詳細討論本發明各實施方式。然而，此實施方式可為各種發明概念的應用，可被具體實行在各種不同的特定範圍內。特定的實施方式是僅以說明為目的，且不受限於揭露的範圍。 Various embodiments of the present invention are discussed in greater detail below. However, this embodiment can be an application of various inventive concepts and can be embodied in various specific scopes. The specific embodiments are for illustrative purposes only, and are not intended to limit the scope of the disclosure.
請參考第1圖，其係繪示本發明之一實施方式之一種複合式固體鹼觸媒的製備方法100的步驟流程圖。必須說明的是，前述複合式固體鹼觸媒的製備方法主要係採用共沉澱法(Co-precipitation)來製備，其包含步驟110、步驟120、步驟130以及步驟140。
Please refer to FIG. 1 , which is a flow chart showing the steps of a
步驟110為進行一溶液準備步驟，其係將一催化
活性成分前驅物作為一前驅物溶液，其中前驅物溶液含有一鎂離子以及一鋁離子。具體而言，催化活性成分前驅物可為但不限於硝酸鎂(Mg(NO3)2．6H2O)與硝酸鋁(Al(NO3)3．9H2O)之混合液，而在前驅物溶液中，鎂離子與鋁離子的莫耳比可為但不限於2至10，藉此，可透過鎂離子與鋁離子的比例不同，以配置出不同鎂鋁比之複合式固體鹼觸媒。
步驟120為進行一滴定步驟，其係將前驅物溶液以一逆向滴定的方式滴入一氨水溶液中，並均勻攪拌形成一觸媒母液，其中前驅物溶液的滴定速率可為0.5滴/秒，且待滴定完成後的觸媒母液之pH值可大於或等於10。詳細來說，逆向滴定係將前驅物溶液滴入鹼液中，由於沉澱劑過量，因此較容易使鎂鋁離子同時且均勻的沉澱下來，以形成鎂鋁複合物。相反地，順向滴定則係將鹼液滴入前驅物溶液中，由於滴入之沉澱劑液滴會被大量的金屬鹽溶液稀釋，因此溶度積小的離子(例如：鋁)會優先沉澱析出，導致鎂鋁離子具有分別沉澱的現象發生。
步驟130為進行一熟化步驟，其係將觸媒母液進行熟化以形成一觸媒前驅物。詳細來說，在調整前驅物溶液的pH值大於或等於10之後，便可將熟化溫度控制在30℃至50℃之範圍內，以熟化10小時至12小時。再者，後續可進行將熟化後之觸媒前驅物真空過濾除水並以去離子水清洗之純化步驟，以及將純化後之觸媒前驅物放置於烘箱中乾燥過夜之乾燥步驟，但本發明不以此為限。
步驟140為進行一鍛燒步驟，其係將觸媒前驅物於一流動空氣下鍛燒，以得到複合式固體鹼觸媒。詳細來說，鍛燒步驟之溫度可為500℃至600℃，並以50mL/min至500mL/min之流量通入空氣，以確保有足夠的氣體可供觸媒前驅物進行鍛燒並氧化形成複合式固體鹼觸媒，此時本發明之複合式固體鹼觸媒為氧化鎂-氧化鋁複合式固體鹼觸媒。
據此，本發明進一步提供一種由前述製備方法製備而得之複合式固體鹼觸媒，其可用以催化甲醇及環氧丙烷以合成丙二醇甲醚。以下將進一步配合第2圖說明應用前述複合式固體鹼觸媒之丙二醇甲醚的合成方法200，且其方法包含步驟210與步驟220。
Accordingly, the present invention further provides a composite solid base catalyst prepared by the aforementioned preparation method, which can be used to catalyze methanol and propylene oxide to synthesize propylene glycol methyl ether. The
步驟210係提供前述複合式固體鹼觸媒，接著步驟220係進行一開環醚化反應，其係於一反應器中，以複合式固體鹼觸媒作為催化劑，將甲醇與環氧丙烷進行開環醚化反應，以得到丙二醇甲醚，其中反應器可為連續式高壓固定床反應器或高溫高壓反應釜式批次反應器。藉此，本發明之複合式固體鹼觸媒可用於連續式高壓固定床反應器與高溫高壓反應釜式批次反應器，以此建立量化分析轉化率與選擇率的關聯性模型，詳細細節詳述於後續實施例，在此便不再贅述。
茲以下列具體實施例進一步示範說明本發明，用以有利於本發明所屬技術領域通常知識者，可在不需過度解讀的情形下完整利用並實踐本發明，而不應將這些實施例 視為對本發明範圍的限制，但用於說明如何實施本發明的材料及方法。 The following specific examples are hereby used to further demonstrate the present invention, so as to help those skilled in the art to which the present invention pertains to fully utilize and practice the present invention without excessive interpretation. It is considered to limit the scope of the invention, but to illustrate how to practice the materials and methods of the invention.
<實施例> <Example>
<複合式固體鹼觸媒之製備與材料性能分析> <Preparation and Material Properties Analysis of Composite Solid Alkali Catalyst>
本發明之複合式固體鹼觸媒是以第1圖之複合式固體鹼觸媒的製備方法100之步驟110至步驟140所製備而得。首先，將已知濃度的Mg(NO3)2．6H2O以及Al(NO3)3．9H2O溶於100mL的去離子水中，以形成前驅物溶液，並倒入滴定管備用。接著，取過量之氨水與去離子水互溶於燒杯中，將配置好的前驅物溶液以0.5滴/秒之速率滴入氨水溶液中，並同時以攪拌機400rpm之轉速在室溫下均勻攪拌，以形成觸媒母液。
The composite solid base catalyst of the present invention is prepared by the
待滴定完成且觸媒母液之pH值大於或等於10之後，將觸媒母液靜置於40℃的油浴中熟化12小時，以形成觸媒前驅物，之後，將觸媒前驅物以真空過濾除水，再以去離子水清洗數次，接著將清洗後之濾餅置於100℃烘箱中乾燥過夜。最後，將乾燥後的觸媒前驅物放入高溫爐，以500℃及600℃鍛燒4至5小時，並同時通入流動空氣(50mL/min至500mL/min)，以合成出氧化鎂-氧化鋁複合式固體鹼觸媒。 After the titration is completed and the pH value of the catalyst mother solution is greater than or equal to 10, the catalyst mother solution is placed in an oil bath at 40°C for 12 hours to mature to form a catalyst precursor. After that, the catalyst precursor is vacuum filtered. After removing water, the filter cake was washed several times with deionized water, and then the filter cake after washing was placed in an oven at 100° C. to dry overnight. Finally, put the dried catalyst precursor into a high-temperature furnace, calcined at 500 ° C and 600 ° C for 4 to 5 hours, and at the same time pass in flowing air (50 mL/min to 500 mL/min), to synthesize magnesium oxide- Alumina composite solid base catalyst.
本發明之複合式固體鹼觸媒，可藉由調控組成比例與操作條件(鍛燒溫度)來控制活性金屬之晶徑與金屬表面積，以達到複合式固體鹼觸媒之高催化活性、選擇性與穩定性。其中複合式固體鹼觸媒之材料性能分析是利用比表 面積與孔隙度分析儀和化學吸附儀分析複合式固體鹼觸媒之比表面積以及孔徑分布，X光繞射儀(X-ray Diffraction,XRD)分析複合式固體鹼觸媒之晶徑以及場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope,FESEM)與能量色散X射線譜(Energy Dispersive X-ray Spectrometer,EDS)分析複合式固體鹼觸媒之型態及元素分布，並進行條件優化測試、選擇性測試、活性測試以及穩定性測試。 The composite solid base catalyst of the present invention can control the crystal diameter and metal surface area of the active metal by adjusting the composition ratio and operating conditions (calcination temperature), so as to achieve high catalytic activity and selectivity of the composite solid base catalyst. and stability. Among them, the material performance analysis of the composite solid alkali catalyst is based on the comparison table. Area and porosity analyzers and chemical adsorption analyzers were used to analyze the specific surface area and pore size distribution of the composite solid base catalyst, and X-ray Diffraction (XRD) was used to analyze the crystal diameter and field emission of the composite solid base catalyst. Scanning electron microscope (Field Emission Scanning Electron Microscope, FESEM) and Energy Dispersive X-ray Spectrometer (Energy Dispersive X-ray Spectrometer, EDS) analyze the type and element distribution of composite solid alkali catalyst, and carry out condition optimization test, selection sex, liveness, and stability tests.
本發明之實施例1至實施例9是以不同鎂鋁莫耳比以及鍛燒溫度來觀察複合式固體鹼觸媒材料性能的影響，其調控條件如下表一所示。 Examples 1 to 9 of the present invention use different magnesium-aluminum molar ratios and calcination temperatures to observe the influence of the performance of the composite solid alkali catalyst material, and the control conditions are shown in Table 1 below.
請參照第3A圖以及第3B圖，其中第3A圖繪示實施例1至實施例5以及比較例1的孔徑分布圖，第3B 圖繪示實施例6至實施例9以及比較例2的孔徑分布圖，而比較例1為鍛燒溫度500℃之商用MgO觸媒，比較例2為鍛燒溫度600℃之商用MgO觸媒。另外，根據第3A圖以及第3B圖，將實施例1至實施例9以及比較例1至比較例2的比表面積(SBET)與平均孔徑的結果列於下表二。 Please refer to Fig. 3A and Fig. 3B, wherein Fig. 3A shows the pore size distribution of Examples 1 to 5 and Comparative Example 1, and Fig. 3B shows the pore size of Examples 6 to 9 and Comparative Example 2 distribution diagram, and Comparative Example 1 is a commercial MgO catalyst with a calcination temperature of 500°C, and Comparative Example 2 is a commercial MgO catalyst with a calcination temperature of 600°C. In addition, according to Fig. 3A and Fig. 3B, the results of the specific surface area (S BET ) and average pore diameter of Examples 1 to 9 and Comparative Examples 1 to 2 are listed in Table 2 below.
由表二的結果可見，在相同鍛燒溫度下，實施例1至實施例5的比表面積較比較例1大，且實施例6至實施例9的比表面積較比較例2大，可證明複合式鎂鋁固體鹼觸媒的比表面積較一般商用MgO鹼性觸媒來得高，而在相同鎂鋁莫耳比下，實施例1及實施例2的比表面積分別大 於實施例8及實施例9的比表面積，可知提高鍛燒溫度後，會造成觸媒比表面積下降，且在整體上平均孔徑會隨溫度與鎂鋁莫耳比的增加而有上升趨勢。 It can be seen from the results in Table 2 that, under the same calcination temperature, the specific surface areas of Examples 1 to 5 are larger than those of Comparative Example 1, and the specific surface areas of Examples 6 to 9 are larger than those of Comparative Example 2, which can be proved to be compounded. The specific surface area of the magnesium-aluminum solid alkali catalyst of the formula is higher than that of the general commercial MgO alkaline catalyst, and under the same magnesium-aluminum molar ratio, the specific surface areas of Example 1 and Example 2 are respectively larger From the specific surface area of Example 8 and Example 9, it can be seen that after increasing the calcination temperature, the specific surface area of the catalyst will decrease, and the overall average pore size will increase with the increase of temperature and magnesium-aluminum molar ratio.
請參照第4A圖以及第4B圖，其中第4A圖繪示實施例1至實施例5以及比較例1的XRD繞射分析圖，第4B圖繪示實施例6至實施例9的XRD繞射分析圖。由第4A圖以及第4B圖的結果可見，在2θ為44°、63°和78°時，有MgO的晶體繞射峰，而在2θ為37°和65°時，有γ-Al2O3的晶體繞射峰，且MgO與γ-Al2O3的晶體繞射峰強度與其對應含量成正比關係。另外，藉由分析X光繞射峰的波形來估計2θ為78°和44°時，MgO的晶徑(dc,MgO)，如下表三所示，並由上述分析結果可知，MgO晶徑會隨鎂鋁莫耳比提升而增大，而鍛燒溫度對於MgO晶徑影響較小。 Please refer to FIG. 4A and FIG. 4B , wherein FIG. 4A shows the XRD diffraction analysis diagrams of Example 1 to Example 5 and Comparative Example 1, and FIG. 4B shows the XRD diffraction analysis diagram of Example 6 to Example 9 diagram. From the results of Figure 4A and Figure 4B, it can be seen that when 2θ is 44°, 63° and 78°, there are crystal diffraction peaks of MgO, and when 2θ is 37° and 65°, there are γ-Al 2 O 3 crystal diffraction peak, and the crystal diffraction peak intensity of MgO and γ-Al 2 O 3 is proportional to their corresponding content. In addition, by analyzing the waveform of the X-ray diffraction peak, the crystal diameters (d c, MgO ) of MgO were estimated when 2θ was 78° and 44°, as shown in Table 3 below. It will increase with the increase of magnesium-aluminum molar ratio, and the calcination temperature has little effect on the crystal diameter of MgO.
請參閱第5A圖以及第5B圖，其中第5A圖繪示實施例1、實施例2、實施例4、實施例5以及比較例1的程溫脫附反應分析圖(CO2-TPD)，第5B圖繪示實施例6至實施例9以及比較例2至比較例3的程溫脫附反應分析圖(CO2-TPD)，而比較例3為鍛燒溫度600℃之Al2O3觸媒。由第5A圖可知，當鎂鋁莫耳比從實施例1增加至實施例5時，鹼基β峰隨著鎂鋁莫耳比的提升而減弱，另外，由第5B圖可知，當鎂鋁莫耳比從實施例6增加至100%鎂之比較例2時，δ中強鹼減弱且γ強鹼變強。另外，藉由CO2-TPD的分析來得到鹼度定量分析，如下表四所示，顯示隨著鎂鋁莫耳比的提升，β鹼基位數有減少的趨勢。 Please refer to Fig. 5A and Fig. 5B, wherein Fig. 5A shows the analysis diagram of temperature-dependent desorption reaction (CO 2 -TPD) of Example 1, Example 2, Example 4, Example 5 and Comparative Example 1, Figure 5B shows the temperature-dependent desorption reaction analysis diagram (CO 2 -TPD) of Examples 6 to 9 and Comparative Examples 2 to 3, and Comparative Example 3 is Al 2 O 3 with a calcination temperature of 600°C catalyst. It can be seen from Figure 5A that when the magnesium-aluminum molar ratio increases from Example 1 to Example 5, the base beta peak decreases with the increase of the magnesium-aluminum molar ratio. In addition, it can be seen from Figure 5B that when the magnesium-aluminum molar ratio increases When the molar ratio was increased from Example 6 to Comparative Example 2 with 100% magnesium, the strong base in delta weakened and the strong base in gamma became stronger. In addition, the quantitative analysis of basicity was obtained by the analysis of CO 2 -TPD, as shown in Table 4 below, which showed that with the increase of the magnesium-aluminum molar ratio, the number of β bases tended to decrease.
接著，可運用Hammett Titration作正交比較，如下表五所示，當鎂鋁莫耳比從實施例2增加至實施例5時，中強鹼均會減弱，總鹼度(total basicity)隨著鎂鋁莫耳比的上升而減少。 Next, Hammett Titration can be used for orthogonal comparison, as shown in Table 5 below, when the magnesium-aluminum molar ratio is increased from Example 2 to Example 5, the medium and strong bases are weakened, and the total basicity increases with The magnesium-aluminum molar ratio increases and decreases.
請參照第6A圖以及第6B圖，其中第6A圖繪示實施例2的FESEM表面形貌，第6B圖繪示實施例2的EDS能量分散光譜圖。由第6A圖以及第6B圖可見，實施例2中的鎂、鋁皆均勻分散在不規則型態的觸媒中，可證明本發明之複合式固體鹼觸媒具有優異的均勻度。 Please refer to FIG. 6A and FIG. 6B , wherein FIG. 6A shows the FESEM surface morphology of Example 2, and FIG. 6B shows the EDS energy dispersion spectrum of Example 2. It can be seen from Figure 6A and Figure 6B that the magnesium and aluminum in Example 2 are uniformly dispersed in the irregular catalyst, which proves that the composite solid alkali catalyst of the present invention has excellent uniformity.
<複合式固體鹼觸媒之條件優化測試平台> <Condition optimization test platform for composite solid alkali catalyst>
首先，將共沉澱製得之複合式固體鹼觸媒倒進壓錠模組約七分滿，用柱塞將觸媒壓至底部，接著，用手動液壓薄片機壓錠，壓至0~3公噸重，最後將柱塞把觸媒從模組底部壓出，即可得到壓錠後的觸媒。 First, pour the composite solid alkali catalyst obtained by co-precipitation into the ingot pressing module about 70% full, press the catalyst to the bottom with a plunger, and then press the ingot with a manual hydraulic flake machine to a weight of 0~3 metric tons , and finally press the plunger to push the catalyst out from the bottom of the module to get the catalyst after pressing.
之後，取17.3克的甲醇以及6.2克的環氧丙烷(莫耳比為5：1)，並與特定比例(3wt%~40wt%)之壓錠後的複合式固體鹼觸媒一同倒入250mL的高壓反應釜中， 接著通入氮氣至反應壓力25kgf/cm2，隨後升溫至設定溫度150℃並反應1小時，反應結束後，待內溫低於反應物之沸點再取樣。 After that, take 17.3 grams of methanol and 6.2 grams of propylene oxide (molar ratio of 5:1), and pour them into 250 mL of compound solid base catalyst after pressing with a specific ratio (3wt%~40wt%). In the autoclave, nitrogen was then introduced to the reaction pressure of 25kgf/cm 2 , then the temperature was raised to a set temperature of 150°C and the reaction was performed for 1 hour. After the reaction was completed, the internal temperature was lower than the boiling point of the reactant before sampling.
請參照第7圖以及第8圖，其中第7圖繪示實施例1至實施例5的環氧丙烷轉化率與丙二醇甲醚選擇率的曲線圖，第8圖繪示不同壓錠強度之觸媒的環氧丙烷轉化率與丙二醇甲醚選擇率的曲線圖。由第7圖的結果可見，在觸媒含量為20wt%之實施例2時，可以達到接近98%的環氧丙烷轉化率，且丙二醇甲醚選擇率亦可達到90%，因此可藉由調整複合式固體鹼觸媒中的鎂鋁莫耳比，來優化觸媒的條件，而由第8圖的結果可見，若使用粉體狀態之觸媒時(壓錠強度為0)，其環氧丙烷轉化率與丙二醇甲醚選擇率較高，但隨著壓錠強度增強後，不論是環氧丙烷轉化率或丙二醇甲醚選擇率皆會降低，故可以加大觸媒量來克服此問題，因此造粒條件亦會影響到觸媒的催化活性。 Please refer to Fig. 7 and Fig. 8, wherein Fig. 7 shows the graph of propylene oxide conversion and propylene glycol methyl ether selectivity in Examples 1 to 5, and Fig. 8 shows catalysts with different pressing strengths Plot of propylene oxide conversion versus propylene glycol methyl ether selectivity. It can be seen from the results in Figure 7 that when the catalyst content is 20wt% in Example 2, the conversion rate of propylene oxide can reach nearly 98%, and the selectivity of propylene glycol methyl ether can also reach 90%, so it can be adjusted by adjusting The magnesium-aluminum molar ratio in the composite solid base catalyst is used to optimize the conditions of the catalyst. From the results in Figure 8, it can be seen that if the catalyst in powder state is used (the ingot strength is 0), its propylene oxide The conversion rate and the selectivity of propylene glycol methyl ether are relatively high, but with the enhancement of the tablet strength, both the conversion rate of propylene oxide and the selectivity of propylene glycol methyl ether will decrease, so the amount of catalyst can be increased to overcome this problem. The particle conditions also affect the catalytic activity of the catalyst.
<複合式固體鹼觸媒之活性與穩定性測試平台> <Activity and Stability Test Platform of Composite Solid Alkali Catalyst>
首先，將上述壓錠後的觸媒打碎，再將打碎後的觸媒粉體進行壓錠，使用手動液壓薄片機壓至10公噸重，所做出來的壓錠片再進行打碎，並先後通過兩種不同尺寸的篩網，其中一個為8-12mesh，另一個為20-25mesh，所篩出來的顆粒小且均勻。 First, crush the above-mentioned ingot-pressed catalyst, then ingot the crushed catalyst powder, and press it to a weight of 10 metric tons using a manual hydraulic flake machine. Two different sizes of sieves, one is 8-12mesh and the other is 20-25mesh, the sieved particles are small and uniform.
之後，將上述觸媒顆粒(12克至34克)填入觸媒床中，接著開啟高壓送液幫浦，將預先配置莫耳比為5：1之甲醇及環氧丙烷溶液送入固定床反應器中，直至反應物 從背壓閥流出後提升背壓閥之壓力指數，並通入氮氣至反應壓力為25kgf/cm2，並待反應器之壓力指數也達到25kgf/cm2，調控高壓送液幫浦之進料流率至設定值(0.4mL/min至2mL/min)。隨後，先以預熱器預熱至110℃至130℃，再升溫反應器至反應溫度145℃至150℃,待達到設定溫度後，開始反應12小時，並在不同的時間點取樣以進行後續產物分析。 After that, the above catalyst particles (12g to 34g) were filled into the catalyst bed, and then the high-pressure liquid feeding pump was turned on, and the methanol and propylene oxide solution pre-configured with a molar ratio of 5:1 was sent into the fixed bed In the reactor, until the reactant flows out from the back pressure valve, the pressure index of the back pressure valve is increased, and nitrogen gas is introduced to the reaction pressure until the reaction pressure is 25kgf/cm 2 , and the pressure index of the reactor also reaches 25kgf/cm 2 , and the high pressure is regulated. The feed flow rate of the liquid feeding pump is set to the set value (0.4mL/min to 2mL/min). Subsequently, the preheater was used to preheat to 110°C to 130°C, and then the reactor was heated to a reaction temperature of 145°C to 150°C. After reaching the set temperature, the reaction was started for 12 hours, and samples were taken at different time points for subsequent follow-up. Product analysis.
請參照第9圖，其係繪示實施例2於不同反應時間下的環氧丙烷轉化率與丙二醇甲醚選擇率的曲線圖。在第9圖的測試中，實施例2之顆粒大小為20-25mesh，觸媒量為34克，預熱溫度為110℃，反應溫度為150℃，反應時間為12小時，進料流率為0.4mL/min，且各反應時間所對應之環氧丙烷轉化率以及丙二醇甲醚選擇率如下表六所示，由此可見，環氧丙烷轉化率會隨著反應時間增加，反應6小時後即可達到99%轉化率且趨於穩定，且丙二醇甲醚選擇率亦達標。 Please refer to FIG. 9 , which is a graph showing the conversion of propylene oxide and the selectivity of propylene glycol methyl ether under different reaction times in Example 2. In the test of Fig. 9, the particle size of Example 2 was 20-25 mesh, the catalyst amount was 34 g, the preheating temperature was 110°C, the reaction temperature was 150°C, the reaction time was 12 hours, and the feed flow rate was 0.4mL/min, and the propylene oxide conversion rate and propylene glycol methyl ether selectivity corresponding to each reaction time are shown in Table 6 below. It can be seen that the propylene oxide conversion rate will increase with the reaction time, and the reaction will be after 6 hours. The conversion rate can reach 99% and tend to be stable, and the selectivity of propylene glycol methyl ether also reaches the standard.
另外，將上述各反應時間之實施例2進行ICP-OES分析，其所析出的鎂離子與鋁離子濃度如下表七所示，並測試二次。由此可見，本發明之複合式固體鹼觸媒中的鎂離子與鋁離子的析出量少，故具有高化學穩定性。 In addition, ICP-OES analysis was performed on Example 2 of each of the above reaction times, and the concentrations of magnesium ions and aluminum ions precipitated were shown in Table 7 below, and were tested twice. It can be seen that the precipitation amount of magnesium ions and aluminum ions in the composite solid alkali catalyst of the present invention is small, so it has high chemical stability.
另外，將本發明之共沉澱法(逆向滴定)與尿素法所製備之複合式固體鹼觸媒之比較結果列於下表八，其中實施例9係以共沉澱法製得，比較例4係以尿素法製得，並在相同丙二醇甲醚的合成方法之條件下進行反應。由表八的結果可見，在相同的丙二醇甲醚合成方法之條件下，比較例4之觸媒活性較實施例9差，轉化率下降約30%，選擇率也略下降，可證明本發明利用逆向滴定之共沉澱法製備觸媒相較於尿素法具有較高的活性。 In addition, the comparison results of the composite solid base catalyst prepared by the co-precipitation method (reverse titration) of the present invention and the urea method are listed in Table 8 below, wherein Example 9 is prepared by the co-precipitation method, and Comparative Example 4 is prepared by using the co-precipitation method. It is prepared by the urea method, and the reaction is carried out under the conditions of the same synthetic method of propylene glycol methyl ether. As can be seen from the results in Table 8, under the conditions of the same propylene glycol methyl ether synthesis method, the catalyst activity of Comparative Example 4 is worse than that of Example 9, the conversion rate is decreased by about 30%, and the selectivity is also slightly decreased. It can be proved that the present invention utilizes Compared with the urea method, the catalyst prepared by the coprecipitation method of reverse titration has higher activity.
綜上所述，本發明經由共沉澱法製備MgO-Al2O3複合式固體鹼觸媒，並調整鎂鋁莫耳比來優化觸媒配方，且可用於連續式高壓固定床反應器與高溫高壓反應釜式批次反應器，在相對低溫(150℃)與中壓(25atm)下，可達到與勻相鹼觸媒同高的轉化率與高選擇率，此外，本發明之複合式固體鹼觸媒機械強度佳，並具有高操作穩定性與高化學穩定性。 To sum up, the present invention prepares MgO-Al 2 O 3 composite solid base catalyst through co-precipitation method, and adjusts the magnesium-aluminum molar ratio to optimize the catalyst formula, and can be used in continuous high-pressure fixed-bed reactors and high temperature The high-pressure reactor type batch reactor can achieve the same high conversion and high selectivity as the homogeneous alkali catalyst at relatively low temperature (150°C) and medium pressure (25atm). Alkali catalysts have good mechanical strength, high operational stability and high chemical stability.
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. Anyone skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be determined by the scope of the appended patent application.
100:複合式固體鹼觸媒的製備方法 100: the preparation method of composite solid alkali catalyst
110,120,130,140:步驟 110, 120, 130, 140: Steps
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| TW (1) | TWI755128B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315225A (en) * | 2000-03-27 | 2001-10-03 | 北京化工大学 | Compound Mg-Al oxide catalyst for alkoxylation reaction and its preparing process |
| CN103880054A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for synthesizing magnesium-aluminum composite oxides with different densities |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315225A (en) * | 2000-03-27 | 2001-10-03 | 北京化工大学 | Compound Mg-Al oxide catalyst for alkoxylation reaction and its preparing process |
| CN103880054A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for synthesizing magnesium-aluminum composite oxides with different densities |
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| TW202216294A (en) | 2022-05-01 |
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