技术领域technical field
本发明属于新型催化剂领域，具体地，涉及一种酯交换反应催化剂、其制备方法及应用，更具体地，涉及一种由多元醇与碳酸二烷基酯经酯交换反应合成多元醇碳酸酯的催化剂、其制备方法及应用。The invention belongs to the field of novel catalysts, in particular, it relates to a catalyst for transesterification reaction, its preparation method and application, more specifically, it relates to a method for synthesizing polyol carbonate by transesterification reaction between polyol and dialkyl carbonate Catalysts, their preparation and applications.
背景技术Background technique
酯交换反应是指酯与醇在酸性或碱性催化剂催化下生成另一种酯和另一种醇的反应。酯交换反应在工业上有广泛的应用，例如，生物柴油就是由动植物油脂与甲醇或乙醇经酯交换反应而得到的脂肪酸单烷基酯，最典型的是脂肪酸甲酯。酯交换反应过程高效进行的关键是酯交换反应催化剂的选用。随着生物柴油产量的日益剧增，新型高效的酯交换反应催化剂研制引起了广泛关注。另一方面，生物柴油的产业化产生了大量的副产物甘油。据报道，每生产1.0kg生物柴油，将副产0.1kg甘油。因此，实现甘油的高效转化，以促进生物柴油产业化持续发展，显得比较迫切。现已发展了多种甘油转化技术，其中将甘油转化为甘油碳酸酯是研究的热点之一。甘油碳酸酯是一种重要的化工原料，用途广泛，市场前景广阔。以甘油为原料合成甘油碳酸酯的方法主要分为二氧化碳法，一氧化碳法，尿素法和酯交换法等。目前，最有希望实现工业化的路线是酯交换法，尤其是以甘油和碳酸二甲酯为原料合成甘油碳酸酯的方法，具有反应条件温和，甘油转化率高，环境友好，产品易于分离等优势，是工业化生产甘油碳酸酯的首选方法之一。Transesterification refers to the reaction of an ester and an alcohol to form another ester and another alcohol under the catalysis of an acidic or basic catalyst. The transesterification reaction is widely used in industry. For example, biodiesel is the fatty acid monoalkyl ester obtained by the transesterification reaction of animal and vegetable oils and methanol or ethanol, and the most typical one is fatty acid methyl ester. The key to efficient transesterification process is the selection of transesterification catalyst. With the rapid increase of biodiesel production, the development of new and efficient transesterification catalysts has attracted widespread attention. On the other hand, the industrialization of biodiesel produces a large amount of by-product glycerol. It is reported that for every 1.0kg of biodiesel produced, 0.1kg of glycerin will be produced by-product. Therefore, it is urgent to realize the efficient conversion of glycerol to promote the sustainable development of biodiesel industrialization. A variety of glycerol conversion technologies have been developed, among which the conversion of glycerol to glycerol carbonate is one of the research hotspots. Glycerol carbonate is an important chemical raw material with a wide range of uses and a broad market prospect. The methods for synthesizing glycerol carbonate from glycerol are mainly divided into carbon dioxide method, carbon monoxide method, urea method and transesterification method. At present, the most promising route for industrialization is the transesterification method, especially the method of synthesizing glycerol carbonate with glycerin and dimethyl carbonate as raw materials, which has the advantages of mild reaction conditions, high conversion rate of glycerin, environmental friendliness, and easy separation of products. , is one of the preferred methods for the industrial production of glycerol carbonate.
目前用于酯交换反应的催化剂主要包括液体酸或碱催化剂，固体酸或碱催化剂以及脂肪酶等。相对于酶催化剂和液体催化剂，固体催化剂，特别是固体碱催化剂，具有工艺简单，环境污染小，易于回收利用等优势，是比较有前途的酯交换反应催化剂类型。其中氧化钙属于传统固体碱催化剂，因其原料来源广、价格便宜、环境友好以及催化活性较高而得到较多应用。Ochoa-Gomez J.R.等系统考察了氧化钙催化甘油与碳酸二甲酯酯交换合成甘油碳酸酯的催化性能，结果发现，在较好的条件下甘油的转化率可达到95％左右(J.R.Ochoa-Gómez,O.Gómez-Jiménez-Aberasturi,B.Maestro-Madurga,et al.Appl.Catal.A:Gen.366(2009)315–324.)。但是他们也发现氧化钙催化剂在重复使用过程中失活明显，不利于该催化剂的大规模应用。本发明人开发了一种氧化钙基成型催化剂，由以碳酸钙为前驱体的氧化钙和氧化铝复合而成(P.F.Lu,H.J.Wang,K.K.Hu.Chem.Eng.J.228(2013)147–154.)。该方法制得的催化剂在反应温度为80℃，碳酸二甲酯与甘油摩尔比为3:1，催化剂(以氧化钙计)与甘油摩尔比为0.15:1.0，反应时间5h，可以获得95％的甘油转化率。但该催化剂活性还是偏低，达到较高甘油转化率所需反应时间过长；同时，该催化剂抗失活性能也不够好，当第5次重复使用时，甘油转化率小于65％。Catalysts currently used for transesterification mainly include liquid acid or base catalysts, solid acid or base catalysts, and lipase. Compared with enzyme catalysts and liquid catalysts, solid catalysts, especially solid base catalysts, have the advantages of simple process, less environmental pollution, and easy recycling, and are more promising types of transesterification catalysts. Among them, calcium oxide belongs to the traditional solid base catalyst, which is widely used because of its wide source of raw materials, low price, environmental friendliness and high catalytic activity. Ochoa-Gomez J.R. etc. systematically investigated the catalytic performance of calcium oxide catalyzed glycerin and dimethyl carbonate transesterification to synthesize glycerol carbonate, and found that the conversion rate of glycerol can reach about 95% under better conditions (J.R.Ochoa-Gómez , O. Gómez-Jiménez-Aberasturi, B. Maestro-Madurga, et al. Appl. Catal. A: Gen. 366 (2009) 315–324.). However, they also found that the calcium oxide catalyst was significantly deactivated during repeated use, which is not conducive to the large-scale application of the catalyst. The inventors have developed a calcium oxide-based molding catalyst, which is composed of calcium oxide and aluminum oxide with calcium carbonate as a precursor (P.F.Lu, H.J.Wang, K.K.Hu.Chem.Eng.J.228(2013) 147 –154.). The catalyst prepared by this method has a reaction temperature of 80°C, a molar ratio of dimethyl carbonate to glycerol of 3:1, a molar ratio of catalyst (calculated as calcium oxide) to glycerin of 0.15:1.0, and a reaction time of 5 hours, and 95% conversion rate of glycerol. However, the activity of the catalyst is still low, and the reaction time required to achieve a higher conversion rate of glycerol is too long; meanwhile, the anti-deactivation performance of the catalyst is not good enough, and when the catalyst is reused for the fifth time, the conversion rate of glycerol is less than 65%.
发明内容Contents of the invention
针对现有技术的以上缺陷或改进需求，本发明提供了一种酯交换反应催化剂、其制备方法及应用，其目的在于通过将氧化钾-氧化钙复合氧化物与成型粘结剂复合，维持催化剂活性，由此解决现有酯交换反应催化剂活性偏低，抗失活性不佳的技术问题。In view of the above defects or improvement needs of the prior art, the present invention provides a transesterification catalyst, its preparation method and application, the purpose of which is to maintain the catalyst by compounding the potassium oxide-calcium oxide composite oxide with a molding binder Activity, thereby solving the technical problems of low activity and poor deactivation resistance of existing transesterification catalysts.
为实现上述目的，按照本发明的一个方面，提供了一种酯交换反应催化剂，所述催化剂包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积在50m2/g至230m2/g之间，其中氧化钾、氧化钙与成型粘结剂的质量比例在(0.05～0.25):1.0:(0.2～0.8)之间。In order to achieve the above object, according to one aspect of the present invention, a kind of transesterification reaction catalyst is provided, and described catalyst comprises catalytic active component and forming binding agent, and described catalytic active component is potassium oxide-calcium oxide composite oxide, so The forming binder is a porous oxide with a specific surface area between 50m2 /g and 230m2 /g, wherein the mass ratio of potassium oxide, calcium oxide and the forming binder is (0.05-0.25):1.0:( 0.2～0.8).
优选地，所述酯交换反应催化剂，其所述成型粘结剂为高岭土、氧化铝或硅藻土。Preferably, the forming binder of the transesterification catalyst is kaolin, alumina or diatomaceous earth.
按照本发明的另一方面，提供了一种酯交换反应催化剂的制备方法，包括以下步骤：According to another aspect of the present invention, a kind of preparation method of transesterification catalyst is provided, comprising the following steps:
(1)将氧化钾前体、氧化钙前体粉末和成型粘结剂粉末作为原料，将原料均匀分散于水中，使得其中钾元素、钙元素与成型粘结剂的质量比例在(0.06～0.3):1.0:(0.3～1.12)，得到原料混合液；(1) Potassium oxide precursor, calcium oxide precursor powder and molding binder powder are used as raw materials, and the raw materials are uniformly dispersed in water so that the mass ratio of potassium element, calcium element and molding binder is (0.06～0.3 ):1.0:(0.3～1.12), to obtain the raw material mixture;
(2)向步骤(1)中的原料混合液中，加入辅剂，均匀混合后干燥研磨，得到粉末A；所述辅剂包括扩孔剂，扩孔剂占原料质量的2％至5％；(2) Add an auxiliary agent to the raw material mixture in step (1), dry and grind after uniform mixing to obtain powder A; the auxiliary agent includes a pore-enlarging agent, and the pore-enlarging agent accounts for 2% to 5% of the mass of the raw material ;
(3)向步骤(2)中获得的粉末A中加入成型助剂，挤压成型并干燥，得到催化剂前体；(3) Adding a molding aid to the powder A obtained in step (2), extruding and drying to obtain a catalyst precursor;
(4)将步骤(3)中获得的催化剂前体，在500℃至900℃下，焙烧3小时至8小时，即得到所述酯交换反应催化剂。(4) Calcining the catalyst precursor obtained in step (3) at 500° C. to 900° C. for 3 hours to 8 hours to obtain the transesterification catalyst.
优选地，所述制备方法，其所述氧化钾前体为氢氧化钾、碳酸钾或硝酸钾；所述氧化钙前体为氢氧化钙、碳酸钙或醋酸钙；所述成型粘结剂为高岭土、氧化铝或硅藻土。Preferably, in the preparation method, the potassium oxide precursor is potassium hydroxide, potassium carbonate or potassium nitrate; the calcium oxide precursor is calcium hydroxide, calcium carbonate or calcium acetate; the forming binder is Kaolin, alumina or diatomaceous earth.
优选地，所述制备方法，其步骤(2)所述扩孔剂为聚丙烯酰胺、活性炭或聚乙二醇，优选为聚丙烯酰胺。Preferably, in the preparation method, the pore-enlarging agent in step (2) is polyacrylamide, activated carbon or polyethylene glycol, preferably polyacrylamide.
优选地，所述制备方法，其步骤(3)所述的成型助剂为质量浓度在20％至30％之间的硅溶胶。Preferably, in the preparation method, the forming aid described in step (3) is silica sol with a mass concentration between 20% and 30%.
优选地，所述制备方法，其步骤(2)中所述辅剂还包括助挤剂，助挤剂占原料质量的2％至5％，所述助挤剂优选为田菁粉。Preferably, in the preparation method, the auxiliary agent in the step (2) further includes an extrusion aid, and the extrusion aid accounts for 2% to 5% of the mass of the raw material, and the extrusion aid is preferably squash powder.
按照本发明的另一方面，提供了一种所述酯交换反应催化剂应用于合成多元醇碳酸酯，所述多元醇碳酸酯符合式(I)的结构According to another aspect of the present invention, it is provided that a kind of said transesterification reaction catalyst is used in the synthesis of polyol carbonate, and said polyol carbonate conforms to the structure of formula (I)
其中，R1表示氢原子或含碳原子数为1～9的直链或含支链的烃基；R2表示含碳原子数为1～9的直链或含支链的烃基。Wherein,R1 represents a hydrogen atom or a straight-chain or branched hydrocarbon group containing 1-9 carbon atoms;R2 represents a straight-chain or branched hydrocarbon group containing 1-9 carbon atoms.
优选地，所述酯交换反应催化剂应用于合成多元醇碳酸酯，其所述多元醇碳酸酯为甘油碳酸酯。Preferably, the transesterification catalyst is used to synthesize polyol carbonate, and the polyol carbonate is glycerol carbonate.
优选地，所述酯交换反应催化剂应用于合成多元醇碳酸酯，其催化温度在65℃～85℃之间，反应原料为碳酸二甲酯与甘油，其摩尔比为1:1至5:1之间，催化剂中氧化钙与甘油摩尔比在0.05:1至0.2:1之间，催化时间1小时至5小时。Preferably, the transesterification catalyst is used in the synthesis of polyol carbonate, the catalytic temperature is between 65°C and 85°C, and the reaction raw materials are dimethyl carbonate and glycerin, and the molar ratio is 1:1 to 5:1 Between, the molar ratio of calcium oxide and glycerol in the catalyst is between 0.05:1 and 0.2:1, and the catalytic time is 1 hour to 5 hours.
总体而言，通过本发明所构思的以上技术方案与现有技术相比，能够取得下列有益效果：Generally speaking, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:
(1)催化活性高，可重复使用多次。本发明提供的成型催化剂对甘油与碳酸二甲酯酯交换合成甘油碳酸酯具有很高的活性，且催化剂在不经煅烧处理的情况下，重复使用10次以后，仍可获得80％以上的甘油转化率。(1) High catalytic activity, can be reused many times. The molded catalyst provided by the invention has high activity for synthesizing glycerol carbonate by transesterification of glycerin and dimethyl carbonate, and the catalyst can still obtain more than 80% of glycerin after being reused 10 times without calcination. Conversion rate.
(2)原料来源广，成本低廉，易于制备。本发明的催化剂的活性组分的前驱体是硝酸钾和碳酸钙，二者原料来源广，价格便宜。催化剂的制备过程主要涉及几种物质的搅拌混合操作，比较简单。(2) The source of raw materials is wide, the cost is low, and the preparation is easy. The precursors of the active components of the catalyst of the present invention are potassium nitrate and calcium carbonate, both of which have wide sources of raw materials and are cheap in price. The preparation process of the catalyst mainly involves the stirring and mixing operation of several substances, which is relatively simple.
(3)不会污染环境和设备。本发明的催化剂的主要成分是钾、钙的氧化物或盐类，对环境友好，且对设备也几乎没有腐蚀。(3) It will not pollute the environment and equipment. The main component of the catalyst of the invention is potassium and calcium oxides or salts, which is friendly to the environment and hardly corrodes equipment.
(4)机械强度高，床层压降小。本发明的催化剂具有固定的形状，具有较高的机械强度，且所形成催化剂床层较粉末催化剂的压降小，适合工业反应器的要求。(4) High mechanical strength and small bed pressure drop. The catalyst of the invention has a fixed shape and high mechanical strength, and the pressure drop of the formed catalyst bed is smaller than that of the powder catalyst, which is suitable for the requirements of industrial reactors.
附图说明Description of drawings
图1是实施例1所制得的酯交换反应催化剂的XRD谱图；Fig. 1 is the XRD spectrogram of the transesterification reaction catalyst that embodiment 1 makes;
图2是实施例10所制得的酯交换反应催化剂的XRD谱图；Fig. 2 is the XRD spectrogram of the transesterification reaction catalyst that embodiment 10 makes;
图3是实施例11所制得酯交换反应催化剂的XRD谱图。Fig. 3 is the XRD spectrogram of the transesterification catalyst prepared in Example 11.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not constitute a conflict with each other.
本发明提供的酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积在50m2/g至230m2/g之间，其中氧化钾、氧化钙与成型粘结剂的质量比例在(0.05～0.25):1.0:(0.2～0.8)之间。所述成型粘结剂优选为高岭土、氧化铝或硅藻土，其中氧化铝常用为活性氧化铝。The transesterification reaction catalyst provided by the invention comprises a catalytically active component and a forming binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the forming binder is a porous oxide with a specific surface area of 50m2 /g to 230m2 /g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is between (0.05-0.25):1.0:(0.2-0.8). The molding binder is preferably kaolin, alumina or diatomaceous earth, wherein alumina is commonly used as activated alumina.
本发明提供的酯交换反应催化剂，其制备方法，包括以下步骤：The transesterification reaction catalyst provided by the invention, its preparation method, comprises the following steps:
(1)将氧化钾前体、氧化钙前体粉末和成型粘结剂粉末作为原料，将原料均匀分散于水中，使得其中钾元素、钙元素与成型粘结剂的质量比例在(0.06～0.3):1.0:(0.3～1.12)，得到原料混合液；所述氧化钾前体为氢氧化钾、碳酸钾或硝酸钾，优选硝酸钾；所述氧化钙前体为氢氧化钙、碳酸钙或醋酸钙，优选碳酸钙；所述成型粘结剂为高岭土、氧化铝或硅藻土，优选氧化铝，常用活性氧化铝。(1) Potassium oxide precursor, calcium oxide precursor powder and molding binder powder are used as raw materials, and the raw materials are uniformly dispersed in water so that the mass ratio of potassium element, calcium element and molding binder is (0.06～0.3 ): 1.0: (0.3～1.12), to obtain the raw material mixture; the potassium oxide precursor is potassium hydroxide, potassium carbonate or potassium nitrate, preferably potassium nitrate; the calcium oxide precursor is calcium hydroxide, calcium carbonate or Calcium acetate, preferably calcium carbonate; the forming binder is kaolin, alumina or diatomaceous earth, preferably alumina, commonly used activated alumina.
(2)向步骤(1)中的原料混合液中，加入辅剂，均匀混合后干燥研磨，得到粉末A；所述辅剂包括扩孔剂，扩孔剂占原料质量的2％至5％；所述扩孔剂为聚丙烯酰胺、活性炭或聚乙二醇，优选为聚丙烯酰胺。干燥时，温度不超过200℃。(2) Add an auxiliary agent to the raw material mixture in step (1), dry and grind after uniform mixing to obtain powder A; the auxiliary agent includes a pore-enlarging agent, and the pore-enlarging agent accounts for 2% to 5% of the mass of the raw material ; The pore-enlarging agent is polyacrylamide, activated carbon or polyethylene glycol, preferably polyacrylamide. When drying, the temperature should not exceed 200°C.
优选地，所述辅剂还包括助挤剂，助挤剂占原料质量的2％至5％，所述助挤剂优选为田菁粉。Preferably, the auxiliary agent also includes an extrusion aid, which accounts for 2% to 5% of the mass of the raw material, and the extrusion aid is preferably squash powder.
(3)向步骤(2)中获得的粉末A中加入成型助剂，挤压成型并干燥，得到催化剂前体；所述的成型助剂为质量浓度在20％至30％之间的硅溶胶。干燥时温度不超过200℃。(3) Add a molding aid to the powder A obtained in step (2), extrude and dry to obtain a catalyst precursor; the molding aid is silica sol with a mass concentration between 20% and 30% . When drying, the temperature should not exceed 200°C.
优选地，将步骤(2)中获得的粉末A，在成型器中挤条成型，并切成的短圆柱状固体。Preferably, the powder A obtained in step (2) is extruded in a molding machine and cut into short cylindrical solid.
(4)将步骤(3)中获得的催化剂前体，在500℃至900℃下，焙烧3小时至8小时，即得到所述酯交换反应催化剂。(4) Calcining the catalyst precursor obtained in step (3) at 500° C. to 900° C. for 3 hours to 8 hours to obtain the transesterification catalyst.
本发明提供的酯交换反应催化剂，应用于合成多元醇碳酸酯，所述多元醇碳酸酯符合式(I)的结构The transesterification catalyst provided by the invention is applied to the synthesis of polyol carbonate, and the polyol carbonate conforms to the structure of formula (I)
其中，R1表示氢原子或含碳原子数为1～9的直链或含支链的烃基；R2表示含碳原子数为1～9的直链或含支链的烃基。该多元醇碳酸酯由多元醇与碳酸二烷基酯经酯交换反应而制得。Wherein,R1 represents a hydrogen atom or a straight-chain or branched hydrocarbon group containing 1-9 carbon atoms;R2 represents a straight-chain or branched hydrocarbon group containing 1-9 carbon atoms. The polyol carbonate is prepared by transesterification of polyol and dialkyl carbonate.
所述多元醇符合式(Ⅱ)的结构Described polyhydric alcohol conforms to the structure of formula (II)
其中，R1表示氢原子或含碳原子数为1～9的直链或含支链的烃基；R2表示含碳原子数为1～9的直链或含支链的烃基。优选地，所述的多元醇为甘油。Wherein,R1 represents a hydrogen atom or a straight-chain or branched hydrocarbon group containing 1-9 carbon atoms;R2 represents a straight-chain or branched hydrocarbon group containing 1-9 carbon atoms. Preferably, the polyhydric alcohol is glycerol.
所述的碳酸二烷基酯符合式(Ⅲ)的结构Described dialkyl carbonate conforms to the structure of formula (Ⅲ)
其中，R3和R4可以相同也可以不同，分别表示含碳原子数为1～9的直链或含支链的烃基。优选地，所述的碳酸二烷基酯为碳酸二甲酯。Wherein, R3 and R4 may be the same or different, and represent straight-chain or branched-chain hydrocarbon groups with 1 to 9 carbon atoms, respectively. Preferably, the dialkyl carbonate is dimethyl carbonate.
优选地，本发明提供的酯交换反应催化剂，应用于合成甘油碳酸酯，催化温度在65℃～85℃之间，反应原料为碳酸二甲酯与甘油，其摩尔比为1:1至5:1之间，所述催化剂中氧化钙与甘油摩尔比在0.05:1至0.2:1之间，催化时间1小时至5小时。所述的甘油碳酸酯结构如式(Ⅳ)所示Preferably, the transesterification catalyst provided by the present invention is applied to the synthesis of glycerol carbonate, the catalytic temperature is between 65°C and 85°C, and the reaction raw materials are dimethyl carbonate and glycerin, and the molar ratio is 1:1 to 5: 1, the molar ratio of calcium oxide to glycerol in the catalyst is between 0.05:1 and 0.2:1, and the catalytic time is 1 hour to 5 hours. Described glycerol carbonate structure is shown in formula (IV)
以下为实施例：The following are examples:
实施例1Example 1
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is activated alumina.
经表征，所得催化剂的机械强度为60N/cm。如图1所示，XRD分析显示催化剂的主要成分是氧化钙，在XRD谱图中未见明显的氧化钾和氧化铝物种特征峰。XRD谱图中硅酸钙物种是由于氧化钙与成型助剂硅溶胶中的二氧化硅反应产生的。After characterization, the mechanical strength of the obtained catalyst was 60N/cm. As shown in Figure 1, XRD analysis shows that the main component of the catalyst is calcium oxide, and there are no obvious characteristic peaks of potassium oxide and aluminum oxide species in the XRD spectrum. The calcium silicate species in the XRD spectrum is due to the reaction of calcium oxide with silica in the silica sol of the forming aid.
所述酯交换反应催化剂，其制备方法，包括以下步骤：Described transesterification catalyst, its preparation method, comprises the following steps:
(1)将氧化钾前体、氧化钙前体粉末和成型粘结剂粉末作为原料，将原料均匀分散于水中，使得其中钾元素、钙元素与成型粘结剂的质量比例为0.17:1.0:0.84，得到原料混合液；所述氧化钾前体为硝酸钾；所述氧化钙前体为碳酸钙；所述成型粘结剂为活性氧化铝。(1) Potassium oxide precursor, calcium oxide precursor powder and molding binder powder are used as raw materials, and the raw materials are evenly dispersed in water so that the mass ratio of potassium element, calcium element and molding binder is 0.17:1.0: 0.84 to obtain a raw material mixture; the potassium oxide precursor is potassium nitrate; the calcium oxide precursor is calcium carbonate; the forming binder is activated alumina.
(2)向步骤(1)中的原料混合液中，加入辅剂，均匀混合后干燥研磨，得到粉末A；所述辅剂包括扩孔剂，扩孔剂占原料质量的3％；所述扩孔剂为聚丙烯酰胺。干燥时，温度为100℃。(2) Add an auxiliary agent to the raw material mixture in step (1), dry and grind after uniform mixing to obtain powder A; the auxiliary agent includes a pore-enlarging agent, which accounts for 3% of the mass of the raw material; The pore expander is polyacrylamide. During drying, the temperature was 100°C.
所述辅剂还包括助挤剂，助挤剂占原料质量的3％，所述助挤剂为田菁粉。The auxiliary agent also includes an extrusion aid, which accounts for 3% of the mass of the raw material, and the extrusion aid is squash powder.
(3)向步骤(2)中获得的粉末A中加入成型助剂，在成型器中挤条成型，切成的短圆柱状固体，并干燥，得到催化剂前体；所述的成型助剂为质量浓度为24％的硅溶胶。干燥时，温度100℃。(3) Add molding aids to the powder A obtained in step (2), extrude in a molding machine, cut into short cylindrical solid, and dried to obtain a catalyst precursor; the forming aid is silica sol with a mass concentration of 24%. When drying, the temperature is 100°C.
(4)将步骤(3)中获得的催化剂前体，在800℃下，焙烧5小时，即得到所述酯交换反应催化剂。(4) Calcining the catalyst precursor obtained in step (3) at 800° C. for 5 hours to obtain the transesterification catalyst.
所述酯交换反应催化剂，应用于合成甘油碳酸酯，催化温度80℃，反应原料为碳酸二甲酯与甘油，其摩尔比为3:1，所用催化剂与甘油摩尔比为0.1:1(以氧化钙计)，催化时间2小时。The transesterification reaction catalyst is applied to the synthesis of glycerol carbonate, the catalytic temperature is 80°C, the reaction raw materials are dimethyl carbonate and glycerin, and the molar ratio thereof is 3:1, and the molar ratio of catalyst and glycerin used is 0.1:1 (in order to oxidize Calcium meter), catalytic time 2 hours.
反应结束后，取出反应产物，用气相色谱分析产品组成，可得甘油转化率为98.54％，甘油碳酸酯收率为84.96％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用15次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为90.52％，甘油碳酸酯收率为86.47％；第10次使用后，甘油转化率为82.56％，甘油碳酸酯收率为77.51％；第15次使用后，甘油转化率为75.27％，甘油碳酸酯收率为71.81％。After the reaction was finished, the reaction product was taken out, and the composition of the product was analyzed by gas chromatography. It was found that the conversion rate of glycerol was 98.54%, and the yield of glycerol carbonate was 84.96%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst is reused 15 times according to the above conditions, and the product composition is analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol is 90.52%, and the yield of glycerol carbonate is 86.47%. After the 10th use, the conversion rate of glycerin The yield of glycerol carbonate was 82.56%, and the yield of glycerol carbonate was 77.51%. After the 15th use, the conversion rate of glycerol was 75.27%, and the yield of glycerol carbonate was 71.81%.
实施例2Example 2
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变氧化钾的前体为碳酸钾。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为99.01％，甘油碳酸酯收率为87.02％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用5次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为77.51％，甘油碳酸酯收率为73.50％。Described transesterification catalyst, its preparation method is identical with embodiment 1, but the precursor of changing potassium oxide is potassium carbonate. The prepared catalyst is used for glycerol and dimethyl carbonate transesterification to synthesize glycerol carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 99.01%, and the yield of glycerol carbonate is 87.02%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst was reused 5 times according to the above conditions, and the product composition was analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol was 77.51%, and the yield of glycerol carbonate was 73.50%.
实施例3Example 3
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变氧化钾的前体为氢氧化钾。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为92.30％，甘油碳酸酯收率为86.15％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用5次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为67.18％，甘油碳酸酯收率为63.65％。Described transesterification catalyst, its preparation method is identical with embodiment 1, but the precursor of changing potassium oxide is potassium hydroxide. The prepared catalyst is used to synthesize glycerol carbonate by transesterification of glycerin and dimethyl carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 92.30%, and the yield of glycerol carbonate is 86.15%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst was reused 5 times according to the above conditions, and the product composition was analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol was 67.18%, and the yield of glycerol carbonate was 63.65%.
实施例4Example 4
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变氧化钙的前体为醋酸钙。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为93.63％，甘油碳酸酯收率为82.02％。Described transesterification catalyst, its preparation method is identical with embodiment 1, but the precursor of changing calcium oxide is calcium acetate. The prepared catalyst is used to synthesize glycerol carbonate by transesterification of glycerin and dimethyl carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 93.63%, and the yield of glycerol carbonate is 82.02%.
实施例5Example 5
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变氧化钙的前体为氢氧化钙。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为88.57％，甘油碳酸酯收率为79.39％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用5次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为64.17％，甘油碳酸酯收率为62.08％。Described transesterification catalyst, its preparation method is identical with embodiment 1, but the precursor of changing calcium oxide is calcium hydroxide. The prepared catalyst is used to synthesize glycerol carbonate by transesterification of glycerol and dimethyl carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 88.57%, and the yield of glycerol carbonate is 79.39%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst was reused 5 times according to the above conditions, and the product composition was analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol was 64.17%, and the yield of glycerol carbonate was 62.08%.
实施例6Example 6
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.05:1.0:0.3。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.05:1.0:0.3. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变硝酸钾和氧化铝的用量，使得其中钾元素、钙元素与成型粘结剂的质量比例为0.06:1.0:0.42。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，可得甘油转化率为93.60％，甘油碳酸酯收率为85.0％。The preparation method of the transesterification catalyst is the same as in Example 1, but the amount of potassium nitrate and aluminum oxide is changed so that the mass ratio of potassium element, calcium element and forming binder is 0.06:1.0:0.42. The prepared catalyst was used to synthesize glycerol carbonate by transesterification between glycerin and dimethyl carbonate, the reaction conditions were the same as those in Example 1, and the conversion rate of glycerol was 93.60%, and the yield of glycerol carbonate was 85.0%.
实施例7Example 7
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.25:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.25:1.0:0.6. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变硝酸钾的用量，使得其中钾元素、钙元素与成型粘结剂的质量比例为0.28:1.0:0.84。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为99.27％，甘油碳酸酯收率为89.64％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用5次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为78.45％，甘油碳酸酯收率为74.94％。The preparation method of the transesterification catalyst is the same as in Example 1, but the amount of potassium nitrate is changed so that the mass ratio of potassium element, calcium element and forming binder is 0.28:1.0:0.84. The prepared catalyst is used for glycerol and dimethyl carbonate transesterification to synthesize glycerol carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 99.27%, and the yield of glycerol carbonate is 89.64%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst was reused 5 times according to the above conditions, and the product composition was analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol was 78.45%, and the yield of glycerol carbonate was 74.94%.
实施例8Example 8
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.2。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.2. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变活性氧化铝的用量，使得其中钾元素、钙元素与成型粘结剂的质量比例为0.17:1.0:0.3。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为99.29％，甘油碳酸酯收率为85.42％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用5次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为91.34％，甘油碳酸酯收率为85.68％。The preparation method of the transesterification catalyst is the same as in Example 1, but the amount of activated alumina is changed so that the mass ratio of potassium element, calcium element and forming binder is 0.17:1.0:0.3. The prepared catalyst is used to synthesize glycerol carbonate by transesterification of glycerol and dimethyl carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 99.29%, and the yield of glycerol carbonate is 85.42%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst was reused 5 times according to the above conditions, and the product composition was analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol was 91.34%, and the yield of glycerol carbonate was 85.68%.
实施例9Example 9
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.8。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.8. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变活性氧化铝的用量，使得其中钾元素、钙元素与成型粘结剂的质量比例为0.17:1.0:1.12。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为99.24％，甘油碳酸酯收率为90.71％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用5次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为76.28％，甘油碳酸酯收率为73.48％。The preparation method of the transesterification catalyst is the same as in Example 1, but the amount of activated alumina is changed so that the mass ratio of potassium element, calcium element and forming binder is 0.17:1.0:1.12. The prepared catalyst is used to synthesize glycerol carbonate by transesterification of glycerol and dimethyl carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 99.24%, and the yield of glycerol carbonate is 90.71%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst was reused 5 times according to the above conditions, and the product composition was analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol was 76.28%, and the yield of glycerol carbonate was 73.48%.
实施例10Example 10
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is activated alumina.
经表征，所得催化剂的机械强度为44N/cm。如图2所示，XRD分析显示催化剂的主要成分是氧化钙，在XRD谱图中未见明显的氧化钾和氧化铝物种特征峰。After characterization, the mechanical strength of the obtained catalyst was 44N/cm. As shown in Figure 2, XRD analysis shows that the main component of the catalyst is calcium oxide, and there are no obvious characteristic peaks of potassium oxide and aluminum oxide species in the XRD spectrum.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变焙烧温度为700℃。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为96.02％，甘油碳酸酯收率为85.29％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用5次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为65.96％，甘油碳酸酯收率为63.30％。The preparation method of the transesterification catalyst is the same as in Example 1, but the calcining temperature is changed to 700°C. The prepared catalyst is used to synthesize glycerol carbonate by transesterification of glycerol and dimethyl carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 96.02%, and the yield of glycerol carbonate is 85.29%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst was reused 5 times according to the above conditions, and the product composition was analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol was 65.96%, and the yield of glycerol carbonate was 63.30%.
实施例11Example 11
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is activated alumina.
经表征，所得催化剂的机械强度为38N/cm。如图3所示，XRD分析显示催化剂的主要成分是氧化钙，在XRD谱图中未见明显的氧化钾和氧化铝物种特征峰。XRD谱图中硅酸钙物种是由于氧化钙与成型助剂硅溶胶中的二氧化硅反应产生的。After characterization, the mechanical strength of the obtained catalyst was 38 N/cm. As shown in Figure 3, XRD analysis shows that the main component of the catalyst is calcium oxide, and there are no obvious characteristic peaks of potassium oxide and aluminum oxide species in the XRD spectrum. The calcium silicate species in the XRD spectrum is due to the reaction of calcium oxide with silica in the silica sol of the forming aid.
所述酯交换反应催化剂，其制备方法与实施例1相同，但改变焙烧温度为900℃。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，用气相色谱分析产品组成，可得甘油转化率为99.33％，甘油碳酸酯收率为89.82％。回收催化剂用50mL甲醇洗涤3次后直接用于下一次反应。按照以上条件将催化剂重复使用5次，并用气相色谱分析产品组成，可得第5次反应后，甘油转化率为75.71％，甘油碳酸酯收率为73.91％。The preparation method of the transesterification catalyst is the same as in Example 1, but the calcining temperature is changed to 900°C. The prepared catalyst is used to synthesize glycerol carbonate by transesterification of glycerin and dimethyl carbonate, the reaction conditions are the same as in Example 1, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 99.33%, and the yield of glycerol carbonate is 89.82%. The recovered catalyst was washed three times with 50 mL of methanol and directly used for the next reaction. The catalyst was reused 5 times according to the above conditions, and the product composition was analyzed by gas chromatography. After the 5th reaction, the conversion rate of glycerol was 75.71%, and the yield of glycerol carbonate was 73.91%.
实施例12Example 12
将实施例1制备的酯交换反应催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，但改变反应温度为75℃。用气相色谱分析产品组成，可得甘油转化率为88.12％，甘油碳酸酯收率为83.18％。The transesterification catalyst prepared in Example 1 was used to transesterify glycerol with dimethyl carbonate to synthesize glycerol carbonate, the reaction conditions were the same as in Example 1, but the reaction temperature was changed to 75°C. The composition of the product was analyzed by gas chromatography, and the conversion rate of glycerol was 88.12%, and the yield of glycerol carbonate was 83.18%.
实施例13Example 13
将实施例1制备的酯交换反应催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例1相同，但改变反应温度为85℃。用气相色谱分析产品组成，可得甘油转化率为99.30％，甘油碳酸酯收率为86.56％。The transesterification catalyst prepared in Example 1 was used to transesterify glycerol with dimethyl carbonate to synthesize glycerol carbonate. The reaction conditions were the same as in Example 1, but the reaction temperature was changed to 85°C. The composition of the product was analyzed by gas chromatography, and the conversion rate of glycerol was 99.30%, and the yield of glycerol carbonate was 86.56%.
实施例14Example 14
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为150m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为高岭土。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of150m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is kaolin.
所述酯交换反应催化剂，其制备方法，包括以下步骤：Described transesterification catalyst, its preparation method, comprises the following steps:
(1)将氧化钾前体、氧化钙前体粉末和成型粘结剂粉末作为原料，将原料均匀分散于水中，使得其中钾元素、钙元素与成型粘结剂的质量比例为0.17:1.0:0.84，得到原料混合液；所述氧化钾前体为硝酸钾；所述氧化钙前体为碳酸钙；所述成型粘结剂为高岭土。(1) Potassium oxide precursor, calcium oxide precursor powder and molding binder powder are used as raw materials, and the raw materials are evenly dispersed in water so that the mass ratio of potassium element, calcium element and molding binder is 0.17:1.0: 0.84 to obtain a raw material mixture; the potassium oxide precursor is potassium nitrate; the calcium oxide precursor is calcium carbonate; the forming binder is kaolin.
(2)向步骤(1)中的原料混合液中，加入辅剂，均匀混合后干燥研磨，得到粉末A；所述辅剂包括扩孔剂，扩孔剂占原料质量的2％；所述扩孔剂为聚乙二醇。干燥时，温度为100℃。(2) Add an auxiliary agent to the raw material mixture in step (1), dry and grind after uniform mixing to obtain powder A; the auxiliary agent includes a pore-enlarging agent, which accounts for 2% of the mass of the raw material; The pore expander is polyethylene glycol. During drying, the temperature was 100°C.
所述辅剂还包括助挤剂，助挤剂占原料质量的2％，所述助挤剂为田菁粉。The auxiliary agent also includes an extrusion aid, which accounts for 2% of the mass of the raw material, and the extrusion aid is squash powder.
(3)向步骤(2)中获得的粉末A中加入成型助剂，在成型器中挤条成型，并切成的短圆柱状固体，并干燥，得到催化剂前体；所述的成型助剂为质量浓度为24％的硅溶胶。干燥时温度为100℃。(3) Add molding aids to the powder A obtained in step (2), extrude in a molding machine, and cut into short cylindrical solid, and dried to obtain a catalyst precursor; the forming aid is silica sol with a mass concentration of 24%. The drying temperature was 100°C.
(4)将步骤(3)中获得的催化剂前体，在800℃下，焙烧3小时，即得到所述酯交换反应催化剂。(4) Calcining the catalyst precursor obtained in step (3) at 800° C. for 3 hours to obtain the transesterification catalyst.
所述酯交换反应催化剂，应用于合成甘油碳酸酯，催化温度在65℃，反应原料为碳酸二甲酯与甘油，其摩尔比为1:1，所述催化剂中氧化钙与甘油摩尔比为0.05:1，催化时间5小时。反应结束后，取出反应产物，用气相色谱分析产品组成，可得甘油转化率为71.13％，甘油碳酸酯收率为62.90％。The transesterification catalyst is applied to the synthesis of glycerol carbonate, the catalytic temperature is 65°C, the reaction raw materials are dimethyl carbonate and glycerin, the molar ratio is 1:1, and the molar ratio of calcium oxide and glycerin in the catalyst is 0.05 : 1, catalytic time 5 hours. After the reaction was finished, the reaction product was taken out, and the composition of the product was analyzed by gas chromatography. It was found that the conversion rate of glycerol was 71.13%, and the yield of glycerol carbonate was 62.90%.
实施例15Example 15
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为50m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.15:1.0:0.6。所述成型粘结剂为硅藻土。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of 50m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.15:1.0:0.6. The molding binder is diatomaceous earth.
所述酯交换反应催化剂，其制备方法，包括以下步骤：Described transesterification catalyst, its preparation method, comprises the following steps:
(1)将氧化钾前体、氧化钙前体粉末和成型粘结剂粉末作为原料，将原料均匀分散于水中，使得其中钾元素、钙元素与成型粘结剂的质量比例为0.17:1.0:0.84，得到原料混合液；所述氧化钾前体为硝酸钾；所述氧化钙前体为碳酸钙；所述成型粘结剂为硅藻土。(1) Potassium oxide precursor, calcium oxide precursor powder and molding binder powder are used as raw materials, and the raw materials are evenly dispersed in water so that the mass ratio of potassium element, calcium element and molding binder is 0.17:1.0: 0.84 to obtain a raw material mixture; the potassium oxide precursor is potassium nitrate; the calcium oxide precursor is calcium carbonate; the forming binder is diatomaceous earth.
(2)向步骤(1)中的原料混合液中，加入辅剂，均匀混合后干燥研磨，得到粉末A；所述辅剂包括扩孔剂，扩孔剂占原料质量的5％；所述扩孔剂为活性炭。干燥时，温度为100℃。(2) Add an auxiliary agent to the raw material mixture in step (1), dry and grind after uniform mixing to obtain powder A; the auxiliary agent includes a pore-enlarging agent, which accounts for 5% of the mass of the raw material; The pore expander is activated carbon. During drying, the temperature was 100°C.
所述辅剂还包括助挤剂，助挤剂占原料质量的5％，所述助挤剂为田菁粉。The auxiliary agent also includes an extrusion aid, which accounts for 5% of the mass of the raw material, and the extrusion aid is squash powder.
(3)向步骤(2)中获得的粉末A中加入成型助剂，在成型器中挤条成型，并切成的短圆柱状固体，并干燥，得到催化剂前体；所述的成型助剂为质量浓度为24％的硅溶胶。干燥时温度为100℃。(3) Add molding aids to the powder A obtained in step (2), extrude in a molding machine, and cut into short cylindrical solid, and dried to obtain a catalyst precursor; the forming aid is silica sol with a mass concentration of 24%. The drying temperature was 100°C.
(4)将步骤(3)中获得的催化剂前体，在800℃下，焙烧8小时，即得到所述酯交换反应催化剂。(4) Calcining the catalyst precursor obtained in step (3) at 800° C. for 8 hours to obtain the transesterification catalyst.
所述酯交换反应催化剂，应用于合成甘油碳酸酯，催化温度在70℃，反应原料为碳酸二甲酯与甘油，其摩尔比为5:1，所述催化剂中氧化钙与甘油摩尔比为0.2:1，催化时间1小时。反应结束后，取出反应产物，用气相色谱分析产品组成，可得甘油转化率为73.46％，甘油碳酸酯收率为71.43％。The transesterification catalyst is applied to the synthesis of glycerol carbonate, the catalytic temperature is 70°C, the reaction raw materials are dimethyl carbonate and glycerin, the molar ratio is 5:1, and the molar ratio of calcium oxide and glycerin in the catalyst is 0.2 : 1, catalytic time 1 hour. After the reaction was finished, the reaction product was taken out, and the composition of the product was analyzed by gas chromatography. It was found that the conversion rate of glycerol was 73.46%, and the yield of glycerol carbonate was 71.43%.
实施例16Example 16
一种酯交换反应催化剂，包括催化活性成分和成型粘结剂，所述催化活性成分为氧化钾-氧化钙复合氧化物，所述成型粘结剂为多孔氧化物，其比表面积为230m2/g，其中氧化钾、氧化钙与成型粘结剂的质量比例为0.05:1.0:0.6。所述成型粘结剂为活性氧化铝。A catalyst for transesterification, comprising a catalytically active component and a shaped binder, the catalytically active component is potassium oxide-calcium oxide composite oxide, and the shaped binder is a porous oxide with a specific surface area of230m2 / g, wherein the mass ratio of potassium oxide, calcium oxide and forming binder is 0.05:1.0:0.6. The molding binder is activated alumina.
所述酯交换反应催化剂，其制备方法与实施例5相同，但改变硝酸钾和氧化铝的用量，使得其中钾元素、钙元素与成型粘结剂的质量比例为0.06:1.0:0.84，并改变焙烧温度为500℃。所制得的催化剂用于甘油与碳酸二甲酯酯交换合成甘油碳酸酯，反应条件与实施例5相同，用气相色谱分析产品组成，可得甘油转化率为85.14％，甘油碳酸酯收率为78.31％。Described transesterification catalyst, its preparation method is identical with embodiment 5, but changes the consumption of potassium nitrate and aluminum oxide, makes wherein the mass ratio of potassium element, calcium element and molding binder is 0.06:1.0:0.84, and changes The firing temperature is 500°C. The prepared catalyst is used to synthesize glycerol carbonate by transesterification of glycerin and dimethyl carbonate, the reaction conditions are the same as in Example 5, and the product composition is analyzed by gas chromatography, and the conversion rate of glycerol is 85.14%, and the yield of glycerol carbonate is 78.31%.
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。Those skilled in the art can easily understand that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, All should be included within the protection scope of the present invention.
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| CN201410576696.2ACN104437455A (en) | 2014-10-24 | 2014-10-24 | Ester-exchange-reaction catalyst, as well as preparation method and application thereof |
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| CN201410576696.2ACN104437455A (en) | 2014-10-24 | 2014-10-24 | Ester-exchange-reaction catalyst, as well as preparation method and application thereof |
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