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CN104801348A - Solid base catalyst for ester exchange reaction and preparation method thereof - Google Patents

Solid base catalyst for ester exchange reaction and preparation method thereof Download PDF

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CN104801348A
CN104801348A CN201510187866.2A CN201510187866A CN104801348A CN 104801348 A CN104801348 A CN 104801348A CN 201510187866 A CN201510187866 A CN 201510187866A CN 104801348 A CN104801348 A CN 104801348A
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nitrate
solid base
organic framework
base catalyst
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CN104801348B (en
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孙林兵
朱丽
刘晓勤
刘定华
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Nanjing Tech University
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Abstract

The invention discloses a solid base catalyst, which is prepared by taking a metal organic framework material as a carrier through the methods of dipping, drying, activating and the like, can be used as a catalyst for ester exchange reaction, and can catalyze the ester exchange reaction to synthesize dimethyl carbonate under mild conditions. The solid base catalyst for the ester exchange reaction is composed of a basic component and a metal organic framework material carrier, wherein the basic component is introduced from a basic precursor, and the mass ratio of the basic precursor to the metal organic framework material is 0.01-0.4: 1.

Description

一种用于酯交换反应的固体碱催化剂及其制备方法A kind of solid base catalyst for transesterification and preparation method thereof

技术领域technical field

本发明涉及一种催化剂及其制备方法,更具体地说涉及一种用于酯交换反应的固体碱催化剂及其制备方法。The invention relates to a catalyst and a preparation method thereof, in particular to a solid base catalyst for transesterification and a preparation method thereof.

背景技术Background technique

碳酸二甲酯(Dimethyl Carbonate,简称DMC)一种备受国内外关注的绿色环保型化工产品,因其结构中含有甲氧基和羰基,有望替代光气等剧毒或致癌物发生羰基化、甲基化及酯交换等反应以制备众多重要化工产品。其合成与应用近年来受到了广泛的重视。DMC的合成路线可分为以下5种:光气法、甲醇氧化羰基化法、酯交换法、甲醇和CO2直接合成法、尿素和甲醇醇解法。光气法由于原料剧毒已逐步被淘汰。目前工业应用的主要为酯交换法和甲醇氧化羰基化法。其中,酯交换法是低放热的温和反应,在液相中进行,过程无腐蚀无毒、选择性高,并且在工艺流程上也最为简单,是极具工业应用前景的方法。Dimethyl Carbonate (Dimethyl Carbonate, referred to as DMC) is a green and environmentally friendly chemical product that has attracted much attention at home and abroad. Methylation and transesterification reactions to prepare many important chemical products. Its synthesis and application have received extensive attention in recent years. The synthesis route of DMC can be divided into the following five kinds: phosgene method, methanol oxidative carbonylation method, transesterification method, methanol and CO2 direct synthesis method, urea and methanol alcoholysis method. The phosgene method has been gradually eliminated due to the highly toxic raw materials. At present, the main industrial applications are transesterification and methanol oxidative carbonylation. Among them, the transesterification method is a mild reaction with low exotherm, which is carried out in the liquid phase. The process is non-corrosive, non-toxic, high in selectivity, and the process is the simplest. It is a method with great industrial application prospects.

工业上酯交换法现用催化剂主要是甲醇钠的甲醇溶液,由于是均相反应,所以反应后该催化剂与产物的分离回收困难,导致成本上升。随着世界环保意识的加强以及绿色化学的发展,人们越来越重视环境友好的催化新工艺过程,以固体碱作为催化剂具有高活性,高选择性,反应条件温和,产物易于分离,可循环使用等诸多优点,所以其研究发展潜力被广泛看好。所以适合于酯交换反应的固体催化剂有待研究开发。The catalyst currently used in the industry for transesterification is mainly methanol solution of sodium methoxide. Since it is a homogeneous reaction, it is difficult to separate and recover the catalyst and the product after the reaction, resulting in an increase in cost. With the strengthening of the world's environmental protection awareness and the development of green chemistry, people pay more and more attention to the new environmentally friendly catalytic process. Using solid base as a catalyst has high activity, high selectivity, mild reaction conditions, easy separation of products, and can be recycled. And many other advantages, so its research and development potential is widely optimistic. Therefore, solid catalysts suitable for transesterification reactions need to be researched and developed.

金属有机骨架材料是近些年发展起来的一种新型材料,它是由无机金属离子和含氮或氧的多齿有机配体通过配位作用自组装形成的具有无限网络结构的多孔材料。其中,(1)ZIFs系列材料(zeolitic imidazolate frameworks)是由Yaghi课题组合成的一系列金属有机骨架材料,它是由金属离子与咪唑或咪唑衍生物络合成的类分子筛咪唑配位聚合物。这类材料与沸石分子筛具有相似的拓扑结构,但在构筑模式上又有别于沸石分子筛,沸石咪唑酯骨架材料是用锌离子和钴离子等取代传统沸石中的硅元素和铝元素,用咪唑或咪唑衍生物取代氧组成的多孔材料。它们都具有较好的热稳定性和化学稳定性,且与传统的分子筛相比,它具有产率较高,微孔尺寸和形状可调、结构和功能多种多样等优点。(2)PCNs系列材料(porous coordination networks)是由美国迈阿密大学Zhou课题组合成出来的。此类材料由于有机配体的不同,孔道、窗口等性质也存在较大差异。(3)PCP系列材料(porous coordination polymers)是由日本京都大学Kitagawa课题组合成的一系列金属有机骨架材料。此系列材料在吸附不同客体分子的过程中会可逆的改变其骨架的结构和性质,出现“gate-opening”现象,这些特性在气体的选择性吸附、分子传感等方面有潜在应用前景。Metal-organic framework material is a new type of material developed in recent years. It is a porous material with an infinite network structure formed by self-assembly of inorganic metal ions and multi-dentate organic ligands containing nitrogen or oxygen through coordination. Among them, (1) ZIFs series materials (zeolitic imidazolate frameworks) are a series of metal-organic framework materials combined by Yaghi's research. It is a molecular sieve-like imidazolate coordination polymer synthesized by the complexation of metal ions and imidazole or imidazole derivatives. This type of material has a similar topology to zeolite molecular sieves, but it is different from zeolite molecular sieves in construction mode. The zeolite imidazolate framework material replaces silicon and aluminum elements in traditional zeolites with zinc ions and cobalt ions, etc., and uses imidazole Or a porous material composed of imidazole derivatives substituted for oxygen. They all have better thermal stability and chemical stability, and compared with traditional molecular sieves, it has the advantages of higher yield, adjustable pore size and shape, and various structures and functions. (2) The PCNs series materials (porous coordination networks) were assembled by the Zhou project of the University of Miami in the United States. Due to the different organic ligands, the properties of such materials such as channels and windows are also quite different. (3) PCP series materials (porous coordination polymers) are a series of metal-organic framework materials combined by Kitagawa, Kyoto University, Japan. This series of materials will reversibly change the structure and properties of their skeletons during the process of adsorbing different guest molecules, and the phenomenon of "gate-opening" will appear. These characteristics have potential applications in the selective adsorption of gases and molecular sensing.

基于上述问题,制备以金属有机骨架材料为载体的高活性固体碱催化剂,并将其应用于酯交换合成碳酸二甲酯的反应具有深远的应用前景和广泛的社会经济效益。Based on the above problems, the preparation of highly active solid base catalysts supported by metal-organic framework materials and their application in the synthesis of dimethyl carbonate by transesterification has far-reaching application prospects and extensive social and economic benefits.

发明内容Contents of the invention

本发明的目的在于提供一种固体碱催化剂,该固体碱催化剂以金属有机骨架材料为载体,通过浸渍、干燥、活化等方法制备得到,可作为酯交换反应的催化剂,并且可在温和条件下催化酯交换反应合成碳酸二甲酯。The object of the present invention is to provide a solid base catalyst, the solid base catalyst is prepared by impregnating, drying, activating and other methods with a metal-organic framework material as a carrier, which can be used as a catalyst for transesterification reaction, and can catalyze Synthesis of dimethyl carbonate by transesterification.

本发明的另一个目的在于提供上述固体碱催化剂的制备方法;同时本发明还提供该催化剂在酯交换反应中的应用。Another object of the present invention is to provide the preparation method of the above-mentioned solid base catalyst; simultaneously the present invention also provides the application of the catalyst in the transesterification reaction.

本发明的目的通过如下技术方案实现:The purpose of the present invention is achieved through the following technical solutions:

本发明的用于酯交换反应的固体碱催化剂,其是由碱性组分及金属有机骨架材料载体构成,所述的碱性组分由碱前驱体引入,碱前驱体与金属有机骨架材料的质量比为0.01~0.4:1。The solid base catalyst for transesterification reaction of the present invention is composed of a basic component and a metal-organic framework material carrier, the basic component is introduced by an alkali precursor, and the alkali precursor and the metal-organic framework material The mass ratio is 0.01-0.4:1.

本发明上述的固体碱催化剂,其进一步的技术方案是所述的碱前驱体为硝酸锂、硝酸钠、硝酸钾、硝酸铷、硝酸铯、硝酸镁、硝酸钙、硝酸锶、硝酸钡及对应的醋酸盐中的一种或几种组成。The above-mentioned solid alkali catalyst of the present invention, its further technical scheme is that described alkali precursor is lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and corresponding One or several components of acetate.

本发明上述的固体碱催化剂,其进一步的技术方案还可以是所述的金属有机骨架材料是型号为ZIF-7、ZIF-8、ZIF-68或ZIF-78的金属有机骨架ZIFs系列材料;或者所述的金属有机骨架材料是型号为PCN-13、PCN-14、PCN-11或HKUST-1金属有机骨架PCNs系列材料及PCP系列材料。The above-mentioned solid base catalyst of the present invention, its further technical scheme can also be that described metal organic framework material is the metal organic framework ZIFs series material that model is ZIF-7, ZIF-8, ZIF-68 or ZIF-78; Or The metal-organic framework material is a PCN-13, PCN-14, PCN-11 or HKUST-1 metal-organic framework PCNs series material and PCP series material.

本发明上述的固体碱催化剂的制备方法,其包括以下步骤:首先将碱前驱体采用湿浸渍法引入,即称取碱前驱体溶解在溶剂中,在搅拌状态下加入金属有机骨架材料,在室温下搅拌1~12h后,在60~90℃水浴中蒸干,在80~120℃烘箱中干燥4~8h,将得到的样品在200~500℃惰性气体氛围中活化1~4h,使之产生碱性位即得到用于酯交换反应的固体碱催化剂。The preparation method of the above-mentioned solid base catalyst of the present invention comprises the following steps: first, introducing the base precursor by wet impregnation method, that is, weighing the base precursor and dissolving it in a solvent, adding metal-organic framework materials under stirring, and stirring at room temperature After stirring at low temperature for 1-12 hours, evaporate to dryness in a water bath at 60-90°C, dry in an oven at 80-120°C for 4-8 hours, and activate the obtained sample in an inert gas atmosphere at 200-500°C for 1-4 hours to produce The basic position obtains the solid base catalyst for the transesterification reaction.

本发明上述的固体碱催化剂的制备方法,其进一步的技术方案是所述的碱前驱体为硝酸锂、硝酸钠、硝酸钾、硝酸铷、硝酸铯、硝酸镁、硝酸钙、硝酸锶、硝酸钡及对应的醋酸盐中的一种或几种组成,碱前驱体与金属有机骨架材料的质量比为0.01~0.4:1。The preparation method of the above-mentioned solid alkali catalyst of the present invention, its further technical scheme is that described alkali precursor is lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and one or more of the corresponding acetates, the mass ratio of the alkali precursor to the metal-organic framework material is 0.01-0.4:1.

本发明上述的固体碱催化剂的制备方法,其进一步的技术方案还可以是所述的金属有机骨架材料是型号为ZIF-7、ZIF-8、ZIF-68或ZIF-78的金属有机骨架ZIFs系列材料;或者所述的金属有机骨架材料是型号为PCN-13、PCN-14、PCN-11或HKUST-1金属有机骨架PCNs系列材料及PCP系列材料。The preparation method of the above-mentioned solid base catalyst of the present invention, its further technical scheme can also be that described metal organic framework material is the metal organic framework ZIFs series that model is ZIF-7, ZIF-8, ZIF-68 or ZIF-78 material; or the metal-organic framework material is PCN-13, PCN-14, PCN-11 or HKUST-1 metal-organic framework PCNs series materials and PCP series materials.

本发明上述的固体碱催化剂的制备方法,其进一步的技术方案还可以是所述的溶剂为去离子水、无水乙醇或无水甲醇中的一种或几种组成;所述的惰性气体为氦气、氩气或氮气。The preparation method of the above-mentioned solid base catalyst of the present invention, its further technical scheme can also be that described solvent is one or more compositions in deionized water, dehydrated alcohol or dehydrated methanol; Described inert gas is Helium, Argon or Nitrogen.

本发明上述的固体碱催化剂可在酯交换反应中进行应用。The above-mentioned solid base catalyst of the present invention can be applied in the transesterification reaction.

本发明上述的固体碱催化剂在酯交换反应中的应用,其进一步的技术方案是在以碳酸乙烯酯和甲醇为原料制备碳酸二甲酯中的应用。The application of the above-mentioned solid base catalyst of the present invention in the transesterification reaction, its further technical scheme is the application in the preparation of dimethyl carbonate with ethylene carbonate and methyl alcohol as raw material.

本发明上述的在以碳酸乙烯酯和甲醇为原料制备碳酸二甲酯的应用主要包括以下步骤:将碳酸乙烯酯、甲醇和固体碱催化剂放入三颈烧瓶中,碳酸乙烯酯和甲醇的摩尔比为1:5,催化剂用量为原料甲醇质量的0.2~5%,反应温度为60~80℃,压力为常压,回流搅拌条件下反应0.5~4h,离心分离得到碳酸二甲酯。The above-mentioned application of the present invention in preparing dimethyl carbonate with ethylene carbonate and methanol as raw materials mainly includes the following steps: ethylene carbonate, methyl alcohol and solid base catalyst are put into a three-necked flask, and the mol ratio of ethylene carbonate and methanol is The ratio is 1:5, the amount of catalyst is 0.2-5% of the mass of raw methanol, the reaction temperature is 60-80°C, the pressure is normal pressure, the reaction is 0.5-4h under the condition of reflux and stirring, and the dimethyl carbonate is obtained by centrifugation.

与现有技术相比发明具有以下有益效果:Compared with the prior art, the invention has the following beneficial effects:

本发明的用于酯交换反应的固体碱催化剂是一种负载型催化剂,由于金属有机骨架材料主要包括ZIFs系列材料、PCNs系列材料及PCP系列材料具有很好的比表面积和丰富的孔结构,制备的催化剂碱性组分高度分散。在酯交换反应以碳酸乙烯酯和甲醇为原料制备碳酸二甲酯的反应中,在温和的反应条件下,活化温度较低,得到的催化剂表现出很好的催化性能。同时,本发明制备方法简单,环境友好,经济节能。The solid base catalyst for the transesterification reaction of the present invention is a supported catalyst, since the metal-organic framework materials mainly include ZIFs series materials, PCNs series materials and PCP series materials have good specific surface area and abundant pore structure, preparation The basic components of the catalyst are highly dispersed. In the reaction of transesterification using ethylene carbonate and methanol as raw materials to prepare dimethyl carbonate, under mild reaction conditions, the activation temperature is low, and the obtained catalyst shows good catalytic performance. At the same time, the preparation method of the invention is simple, environment-friendly, economical and energy-saving.

具体实施方式Detailed ways

本发明用以下具体实施例子说明,但本发明并不限于下述实施例,在不脱离前后所述宗旨的范围内,变化实施都包含在本发明的技术范围内。The present invention is illustrated with the following specific implementation examples, but the present invention is not limited to the following examples. Within the scope of not departing from the purpose described before and after, all changes and implementations are included in the technical scope of the present invention.

实施例1Example 1

称取0.3g的LiNO3溶解在去离子水中,在搅拌状态下加入0.7g的金属有机骨架材料HKUST-1,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于280℃活化2h,从而将LiNO3分解。Weigh 0.3g of LiNO 3 and dissolve it in deionized water, add 0.7g of metal-organic framework material HKUST-1 under stirring, stir at room temperature for 6h, place in 80°C water bath, evaporate to dryness, and then place in 100°C oven After drying for 8 hours, the obtained sample was placed in a U-shaped tube and activated with nitrogen gas at 280°C for 2 hours to decompose LiNO 3 .

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为38.9%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added into the flask, and stirred at 65°C for 4 hours under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 38.9%.

实施例2Example 2

称取0.17g的Mg(NO3)2·6H2O溶解在无水乙醇中,在搅拌状态下加入0.9g的金属有机骨架材料ZIF-8,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于350℃活化2h,从而将Mg(NO3)2分解。Weigh 0.17g of Mg(NO 3 ) 2 ·6H 2 O and dissolve it in absolute ethanol, add 0.9g of metal-organic framework material ZIF-8 under stirring, stir at room temperature for 6h and place in 80°C water bath Evaporate to dryness, and then dry in an oven at 100°C for 8 hours, place the obtained sample in a U-shaped tube and blow nitrogen into it to activate at 350°C for 2 hours, so as to decompose Mg(NO 3 ) 2 .

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为17.9%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added into the flask, and stirred at 65°C for 4h under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 17.9%.

实施例3Example 3

称取0.31g的CH3COOLi·2H2O溶解在无水甲醇中,在搅拌状态下加入0.8g的金属有机骨架材料PCN-14,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于300℃活化2h,从而将CH3COOLi分解。Weigh 0.31g of CH 3 COOLi·2H 2 O and dissolve it in anhydrous methanol, add 0.8g of metal-organic framework material PCN-14 under stirring, stir at room temperature for 6h, and evaporate to dryness in a water bath at 80°C. Then it was dried in an oven at 100°C for 8h, and the obtained sample was placed in a U-shaped tube and activated with nitrogen gas at 300°C for 2h to decompose CH 3 COOLi.

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为35.2%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added into the flask, and stirred at 65°C for 4h under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 35.2%.

实施例4Example 4

称取0.1g的Sr(NO3)2溶解在无水乙醇中,在搅拌状态下加入0.9g的金属有机骨架材料ZIF-8,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于350℃活化2h,从而将Sr(NO3)2分解。Weigh 0.1g of Sr(NO 3 ) 2 and dissolve it in absolute ethanol, add 0.9g of metal-organic framework material ZIF-8 under stirring, stir at room temperature for 6h, place in 80°C water bath and evaporate to dryness, then Dry in an oven at 100°C for 8 hours, place the obtained sample in a U-shaped tube and blow nitrogen into it to activate at 350°C for 2 hours, so as to decompose Sr(NO 3 ) 2 .

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为18.5%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added into the flask, and stirred at 65°C for 4h under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 18.5%.

实施例5Example 5

称取0.2g的CH3COOK溶解在无水乙醇中,在搅拌状态下加入0.8g的金属有机骨架材料ZIF-68,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于300℃活化2h,从而将CH3COOK分解。Weigh 0.2g of CH 3 COOK and dissolve it in absolute ethanol, add 0.8g of metal-organic framework material ZIF-68 under stirring, stir at room temperature for 6h, place it in a water bath at 80°C and evaporate to dryness, then at 100°C After drying in an oven for 8 hours, the obtained sample was placed in a U-shaped tube and activated with nitrogen gas at 300°C for 2 hours to decompose CH 3 COOK.

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为29.7%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added to the flask, and stirred at 65°C for 4 hours under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 29.7%.

实施例6Example 6

称取0.1g的LiNO3溶解在去离子水中,在搅拌状态下加入0.9g的金属有机骨架材料PCN-13,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于250℃活化2h,从而将LiNO3分解。Weigh 0.1g of LiNO 3 and dissolve it in deionized water, add 0.9g of metal-organic framework material PCN-13 under stirring, stir at room temperature for 6h, evaporate to dryness in 80°C water bath, and then place in 100°C oven After drying for 8 hours, the obtained sample was placed in a U-shaped tube and activated with nitrogen gas at 250°C for 2 hours to decompose LiNO 3 .

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为15.3%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added into the flask, and stirred at 65°C for 4h under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 15.3%.

实施例7Example 7

称取0.25g的Ca(NO3)2溶解在无水甲醇中,在搅拌状态下加入0.75g的金属有机骨架材料PCN-11,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于350℃活化2h,从而将Ca(NO3)2分解。Weigh 0.25g of Ca(NO 3 ) 2 and dissolve it in anhydrous methanol, add 0.75g of metal-organic framework material PCN-11 under stirring, stir at room temperature for 6h, place in 80°C water bath and evaporate to dryness, then Dry in an oven at 100°C for 8 hours, place the obtained sample in a U-shaped tube and blow nitrogen into it to activate at 350°C for 2 hours, so as to decompose Ca(NO 3 ) 2 .

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为27.1%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added into the flask, and stirred at 65°C for 4h under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 27.1%.

实施例8Example 8

称取0.33g的CH3COONa·3H2O溶解在去离子水中,在搅拌状态下加入0.8g的金属有机骨架材料HKUST-1,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于300℃活化2h,从而将CH3COONa分解。Weigh 0.33g of CH 3 COONa·3H 2 O and dissolve it in deionized water, add 0.8g of metal-organic framework material HKUST-1 under stirring, stir at room temperature for 6h, place in 80°C water bath and evaporate to dryness, then Dry in an oven at 100°C for 8h, place the obtained sample in a U-shaped tube and blow nitrogen into it to activate at 300°C for 2h, so as to decompose CH 3 COONa.

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为30.1%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added to the flask, and stirred at 65°C for 4 hours under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 30.1%.

实施例9Example 9

称取0.1g的Sr(NO3)2溶解在无水乙醇中,在搅拌状态下加入0.9g的金属有机骨架材料ZIF-7,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于400℃活化2h,从而将Sr(NO3)2分解。Weigh 0.1g of Sr(NO 3 ) 2 and dissolve it in absolute ethanol, add 0.9g of metal-organic framework material ZIF-7 under stirring, stir at room temperature for 6h, place in 80°C water bath and evaporate to dryness, then Dry in an oven at 100°C for 8 hours, place the obtained sample in a U-shaped tube and blow nitrogen into it to activate at 400°C for 2 hours, so as to decompose Sr(NO 3 ) 2 .

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为12.8%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added to the flask, and stirred at 65°C for 4 hours under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 12.8%.

实施例10Example 10

称取0.17g的Mg(NO3)2·6H2O溶解在无水甲醇中,在搅拌状态下加入0.9g的金属有机骨架材料ZIF-78,于室温下搅拌6h后置于80℃水浴中蒸干,然后在100℃烘箱中烘干8h,将得到的样品置于U型管中通入氮气于400℃活化2h,从而将Mg(NO3)2分解。Weigh 0.17g of Mg(NO 3 ) 2 ·6H 2 O and dissolve it in anhydrous methanol, add 0.9g of metal-organic framework material ZIF-78 under stirring, stir at room temperature for 6h and place in 80°C water bath Evaporate to dryness, then dry in an oven at 100°C for 8h, place the obtained sample in a U-shaped tube and blow nitrogen into it to activate at 400°C for 2h, so as to decompose Mg(NO 3 ) 2 .

将16g甲醇,8.7g碳酸乙烯酯和0.08g催化剂加入烧瓶中,常压下,65℃搅拌反应4h,经离心分离得上层清液并用气相色谱分析,DMC的产率为13.7%。16g of methanol, 8.7g of ethylene carbonate and 0.08g of catalyst were added to the flask, and stirred at 65°C for 4 hours under normal pressure. The supernatant was obtained by centrifugation and analyzed by gas chromatography. The yield of DMC was 13.7%.

Claims (10)

1. the solid base catalyst for ester exchange reaction, it is characterized in that this solid base catalyst is made up of basic component and metal-organic framework materials carrier, described basic component is introduced by alkali presoma, and the mass ratio of alkali presoma and metal-organic framework materials is 0.01 ~ 0.4:1.
2. solid base catalyst according to claim 1, is characterized in that described alkali presoma is one or more compositions in the acetate of lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and correspondence.
3. solid base catalyst according to claim 1, is characterized in that described metal-organic framework materials to be model is the metallic organic framework ZIFs series material of ZIF-7, ZIF-8, ZIF-68 or ZIF-78; Or described metal-organic framework materials is model is PCN-13, PCN-14, PCN-11 or HKUST-1 metallic organic framework PCNs series material and PCP series material.
4. according to the preparation method of the arbitrary described solid base catalyst of claim 1-3, it is characterized in that comprising the following steps: first adopted by alkali presoma wet infusion process to introduce, namely take alkali presoma to dissolve in a solvent, metal-organic framework materials is added under stirring, after at room temperature stirring 1 ~ 12h, evaporate to dryness in 60 ~ 90 DEG C of water-baths, dry 4 ~ 8h in 80 ~ 120 DEG C of baking ovens, the sample obtained is activated 1 ~ 4h in 200 ~ 500 DEG C of atmosphere of inert gases, makes it to produce the solid base catalyst that namely basic sites obtains for ester exchange reaction.
5. the preparation method of solid base catalyst according to claim 4, it is characterized in that described alkali presoma is one or more compositions in the acetate of lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and correspondence, the mass ratio of alkali presoma and metal-organic framework materials is 0.01 ~ 0.4:1.
6. the preparation method of the solid base catalyst according to claim 4 or 5, is characterized in that described metal-organic framework materials to be model is the metallic organic framework ZIFs series material of ZIF-7, ZIF-8, ZIF-68 or ZIF-78; Or described metal-organic framework materials is model is PCN-13, PCN-14, PCN-11 or HKUST-1 metallic organic framework PCNs series material and PCP series material.
7. the preparation method of solid base catalyst according to claim 4, is characterized in that described solvent is one or more compositions in deionized water, absolute ethyl alcohol or absolute methanol; Described inert gas is helium, argon gas or nitrogen.
8. one kind as arbitrary in claim 1-3 as described in the application of solid base catalyst in ester exchange reaction.
9. the application of solid base catalyst according to claim 8 in ester exchange reaction, it is characterized in that preparing the application in dimethyl carbonate for raw material with ethylene carbonate and methyl alcohol.
10. the application of solid base catalyst according to claim 9 in ester exchange reaction, it is characterized in that described mainly comprising the following steps in the application preparing dimethyl carbonate for raw material with ethylene carbonate and methyl alcohol: ethylene carbonate, methyl alcohol and solid base catalyst are put into three-neck flask, the mol ratio of ethylene carbonate and methyl alcohol is 1:5, catalyst amount is 0.2 ~ 5% of material benzenemethanol quality, reaction temperature is 60 ~ 80 DEG C, pressure is normal pressure, react 0.5 ~ 4h under return stirring condition, centrifugation obtains dimethyl carbonate.
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CN109603802A (en) * 2018-12-25 2019-04-12 开封中科新材料有限公司 For by urea and the composite catalyst of methanol-fueled CLC dimethyl carbonate and its preparation method and application
CN112724017A (en) * 2021-01-14 2021-04-30 吉林师范大学 Method for synthesizing asymmetric organic carbonate at room temperature
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