技术领域technical field
本发明涉及一种树枝状Cu/C-CuSiO3纳米结构加氢催化剂及其制备方法，该催化剂具有较高的铜金属分散度、稳定的形貌结构和表面Cu(I)/Cu(0)双活性组分，可用于催化加氢反应。The invention relates to a dendritic Cu/C-CuSiO nanostructure hydrogenation catalyst and a preparation method thereof. The catalyst has a high degree of dispersion of copper metal, a stable morphology and surface Cu(I)/Cu(0) Dual active components, can be used to catalyze hydrogenation reaction.
背景技术Background technique
催化加氢是有机反应中最重要的反应之一，对工业生产应用具有重要的意义，而铜基催化剂以其价廉易得而成为众多催化加氢过程主要采用的催化剂。目前工业上应用于加氢反应的铜基催化剂大多采用浸渍法、共沉淀法等传统的负载方法制得，简单的负载型催化剂在制备过程中容易导致活性组分分散度不高、存在于体相组分而未得到最大化的利用。同时，负载于载体表面的活性金属由于弱的载体-金属相互作用，造成金属纳米颗粒易流失、活性组分与结构不稳定，在反应过程中易发生金属晶粒的迁移烧结，而面临反应活性低、稳定性差、反应条件苛刻等问题。此外，表面多价态铜活性组分稳定共存是加氢反应获得高活性的关键，然而，高温氢气氛围下的强还原性，催化剂上铜活性组分在加氢反应中会发生的化学价态变化，使得催化剂活性和稳定性差，因此，研发更加高效稳定的加氢反应催化剂是实现此类反应过程工业应用的关键问题。Catalytic hydrogenation is one of the most important reactions in organic reactions, and it is of great significance to industrial production applications. Copper-based catalysts have become the main catalysts used in many catalytic hydrogenation processes because of their low price and easy availability. At present, most of the copper-based catalysts used in industrial hydrogenation reactions are prepared by traditional loading methods such as impregnation method and coprecipitation method. The preparation process of simple supported catalysts tends to cause low dispersion of active components and exist in the body. phase components without maximizing utilization. At the same time, due to the weak carrier-metal interaction, the active metal loaded on the surface of the carrier is easy to lose the metal nanoparticles, the active components and the structure are unstable, and the migration and sintering of the metal crystal grains are prone to occur during the reaction process, and the reaction activity Low, poor stability, harsh reaction conditions and other issues. In addition, the stable coexistence of multivalent copper active components on the surface is the key to high activity in the hydrogenation reaction. However, the strong reducibility in the high-temperature hydrogen atmosphere, the chemical valence state of the copper active components on the catalyst in the hydrogenation reaction Therefore, the development of more efficient and stable hydrogenation reaction catalysts is a key issue to realize the industrial application of this type of reaction process.
硅酸盐材料由于其结构特征(硅氧四面体，硅原子占据中心，四个氧原子占据四角)，其化学性质稳定，熔点高，因此硅酸盐催化剂具有金属与载体强相互作用和良好的反应稳定性。铜硅催化剂制备中形成的硅酸铜材料对稳定铜催化剂的结构和铜组分具有重要的作用，同时硅酸铜的结构稳定，在中低温条件下很难将铜还原为金属态，因此温度的调控可实现催化剂多价态铜活性组分的共存，通过改变硅酸铜及负载铜的相对量可实现催化剂表面不同价态同比例的调变。此外，芯鞘结构材料近年来在催化材料领域发展迅速，由于其特殊形貌的纳米结构材料，在提升催化剂稳定性方面，其“鞘”组分起到空间限域效应，使得活性金属“芯”组分在尺度上的成长被限定在一定范围内，可阻止原子高温下在表面迁移聚集长大而烧结，活性金属的分散性和稳定性，从而提升催化反应性能。Due to its structural characteristics (silicon-oxygen tetrahedron, silicon atom occupies the center, and four oxygen atoms occupy the four corners), its chemical properties are stable and its melting point is high. Therefore, the silicate catalyst has a strong interaction between the metal and the support and good Response stability. The copper silicate material formed in the preparation of the copper-silicon catalyst plays an important role in stabilizing the structure of the copper catalyst and the copper component. At the same time, the structure of the copper silicate is stable, and it is difficult to reduce copper to a metallic state under medium and low temperature conditions. Therefore, the temperature The adjustment of the catalyst can realize the coexistence of multivalent copper active components of the catalyst, and the modulation of different valence states on the catalyst surface in the same proportion can be realized by changing the relative amount of copper silicate and supported copper. In addition, core-sheath structure materials have developed rapidly in the field of catalytic materials in recent years. Due to their special morphology nanostructure materials, in terms of improving the stability of catalysts, the "sheath" component has a spatial confinement effect, making the active metal "core" "The growth of components on the scale is limited to a certain range, which can prevent atoms from migrating, agglomerating, and sintering on the surface at high temperatures, and the dispersion and stability of active metals, thereby improving the performance of catalytic reactions.
此外，碳纳米材料具有一些独特的结构和物理化学性质，尤其是较高的比表面积、对氢的吸附活化并促进其溢流的优异性能。因此，以碳纳米管作为模板，硅酸铜纳米材料形成的树枝状复合结构催化剂不仅有利于铜活性组分的分散，而且还可以在树枝状结构间固定镶嵌一定量的金属铜纳米颗粒，对于提高铜活性位数量、稳定铜活性组分，减少铜纳米晶粒的迁移烧结有显著作用。In addition, carbon nanomaterials have some unique structural and physicochemical properties, especially high specific surface area, excellent performance in activating hydrogen adsorption and promoting its overflow. Therefore, using carbon nanotubes as a template, the dendritic composite structure catalyst formed by copper silicate nanomaterials is not only conducive to the dispersion of copper active components, but also can fix a certain amount of metallic copper nanoparticles between the dendritic structures. It has a significant effect on increasing the number of copper active sites, stabilizing copper active components, and reducing the migration and sintering of copper nanocrystals.
发明内容Contents of the invention
针对铜基催化剂在高温加氢反应过程中晶粒迁移、烧结和铜活性组分价态不稳定引起失活的问题，本发明应用常规的氧化物、硅酸盐等材料，开发了低成本、操作简单的树枝状芯鞘结构铜基催化剂，耦合树枝状独特形貌结构对催化剂的活性组分的促进作用及其组分之间的协同效应，从而达到提升反应活性和稳定性的目的。Aiming at the problem of deactivation caused by crystal grain migration, sintering and unstable valence state of copper active components during the high-temperature hydrogenation reaction of copper-based catalysts, the present invention uses conventional oxides, silicates and other materials to develop a low-cost, The simple-to-operate dendritic core-sheath structure copper-based catalyst is coupled with the promotion effect of the unique dendritic morphology on the active components of the catalyst and the synergistic effect between the components, so as to achieve the purpose of improving the reactivity and stability.
为了解决上述技术问题，本发明是通过以下技术方案实现的：制备了一种树枝状Cu/C-CuSiO3纳米结构加氢催化剂。在此种具有树枝状芯鞘结构的纳米催化剂中，不同铜活性组分可通过控制还原进行调变，所包覆二氧化硅层的厚度可通过改变所加入的硅源的量进行调控，所包覆硅酸铜层的厚度可通过改变所加入的二价铜离子的量进行调控，负载的活性组分铜的量可通过改变相应前躯体的负载量进行调控。In order to solve the above technical problems, the present invention is achieved through the following technical solutions: a dendritic Cu/C-CuSiO nanostructured hydrogenation catalyst is prepared. In this nanocatalyst with a dendritic core-sheath structure, different copper active components can be adjusted by controlling the reduction, and the thickness of the coated silica layer can be adjusted by changing the amount of silicon source added. The thickness of the coated copper silicate layer can be regulated by changing the amount of added divalent copper ions, and the amount of loaded active component copper can be regulated by changing the loading amount of the corresponding precursor.
本发明提供的树枝状Cu/C-CuSiO3纳米结构加氢催化剂的制备工艺过程，具体步骤是：The preparation process of dendritic Cu/C-CuSiO nanostructure hydrogenation catalyst provided by the invention, concrete steps are:
1)制备CNT@SiO2材料：1) Preparation of CNT@SiO2 material:
0.1-0.3g十六烷基三甲基溴化铵(CTAB)、30-100mL去离子水、120-400mL无水乙醇、 1-4mL质量分数25-28wt％的氨水混合后在室温下搅拌。剧烈搅拌的同时加入一定量碳纳米管CNTs(DI＝5-100nm)，然后进行0.5～3小时的超声分散。向上述悬浊液中滴加0.5-3.5mL 正硅酸乙酯，继续在室温下剧烈搅拌4-16小时。将所得中间产品洗涤。最后，通过离子交换或高温焙烧除去结构导向剂。0.1-0.3g of cetyltrimethylammonium bromide (CTAB), 30-100mL of deionized water, 120-400mL of absolute ethanol, and 1-4mL of ammonia water with a mass fraction of 25-28wt% were mixed and stirred at room temperature. A certain amount of carbon nanotube CNTs (DI=5-100nm) is added while vigorously stirring, and then ultrasonic dispersion is carried out for 0.5-3 hours. Add 0.5-3.5 mL of tetraethyl orthosilicate dropwise to the above suspension, and continue vigorously stirring at room temperature for 4-16 hours. The resulting intermediate product is washed. Finally, the structure directing agent is removed by ion exchange or high temperature calcination.
2)制备Cu/C-yCuSiO3材料：2) Preparation of Cu/C-yCuSiO3 material:
把0.01g-1g CNT@SiO2分散于36-360mL去离子水中，超声分散均匀。在低速搅拌下加入0.2-20mL氨水(质量分数28％)，向上述液体中滴加0.12-12mL浓度为0.01-1M的硝酸铜，搅拌5分钟。把上述悬浊液放入水热釜中于100-180℃下加热4-24小时。自然冷却后多次离心洗涤产品。然后，在40-100℃下干燥完全。Disperse 0.01g-1g CNT@SiO2 in 36-360mL deionized water, and disperse evenly by ultrasonic. Add 0.2-20 mL of ammonia water (28% by mass) under low-speed stirring, add dropwise 0.12-12 mL of copper nitrate with a concentration of 0.01-1 M into the liquid, and stir for 5 minutes. Put the above suspension into a hydrothermal kettle and heat at 100-180°C for 4-24 hours. After natural cooling, the product was washed several times by centrifugation. Then, dry completely at 40-100°C.
3)制备xCu/C-yCuSiO3材料：3) Preparation of xCu/C-yCuSiO3 material:
将0.5g Cu/C-yCuSiO3材料超声分散于125ml溶剂中。向上述液体中加一定量的活性组分Cu，搅拌均匀后于40～60℃下进行旋蒸。彻底蒸干溶剂后在氮气或氩气保护下进行焙烧。0.5 g of Cu/C-yCuSiO material was ultrasonically dispersed in 125 ml of solvent. Add a certain amount of active component Cu to the above liquid, stir evenly, and carry out rotary evaporation at 40-60°C. After evaporating the solvent completely, it is roasted under the protection of nitrogen or argon.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
1、有效地解决了铜基催化剂在高温加氢反应过程中晶粒迁移、烧结和铜活性组分价态不稳定引起失活的问题；1. Effectively solve the problems of deactivation caused by crystal grain migration, sintering and unstable valence state of copper active components during the high-temperature hydrogenation reaction of copper-based catalysts;
2、实现了铜基催化剂中不同铜活性组分比例可调变，还原后催化剂表面的Cu(I)/Cu(0)的相对比例可调；2. The ratio of different copper active components in the copper-based catalyst can be adjusted, and the relative ratio of Cu(I)/Cu(0) on the surface of the catalyst after reduction can be adjusted;
3、催化剂独特的树枝状芯鞘结构使比表面积与孔道体积增大，从而可获得较高的气体通量。3. The unique dendritic core-sheath structure of the catalyst increases the specific surface area and pore volume, thereby obtaining higher gas flux.
附图说明Description of drawings
图1是本发明方法制备树枝状Cu/C-CuSiO3纳米结构加氢催化剂不同步骤的TEM图；Fig. 1 is the TEM figure of the different steps of dendritic Cu/C-CuSiO3 nanostructure hydrogenation catalyst prepared by the inventive method;
图2是本发明方法制备树枝状Cu/C-CuSiO3纳米结构加氢催化剂的TEM图；Fig. 2 is the TEM figure that the inventive method prepares dendritic Cu/C-CuSiO nanostructure hydrogenation catalyst;
图3是不同制备参数下所得到的包硅厚度的统计图及相应的TEM图；Fig. 3 is a statistical diagram and a corresponding TEM diagram of the silicon-coated thickness obtained under different preparation parameters;
图4是采用Cu2p谱和铜的Cu LMM XAES谱表征本发明方法制备的催化剂还原后表面不同的Cu(I)/Cu(0)比例；Fig. 4 adopts the Cu LMM XAES spectrum of Cu2p spectrum and copper to characterize the different Cu(I)/Cu(0) ratios on the surface after the reduction of the catalyst prepared by the inventive method;
具体实施方式(实施例)Specific embodiments (embodiments)
下面结合实施例和附图对本发明作进一步说明。The present invention will be further described below in conjunction with the embodiments and accompanying drawings.
实施例1Example 1
0.16g十六烷基三甲基溴化铵(CTAB)、30mL去离子水、100mL无水乙醇、2mL 质量分数25-28wt％的氨水混合后在室温下搅拌均匀。剧烈搅拌的同时加入0.1g碳纳米管 CNTs(DI＝20-40nm)，然后进行480min的超声分散。向上述悬浊液中滴加正硅酸乙酯的醇溶液(0.6mL TEOS溶于20mL无水乙醇)，继续在室温下剧烈搅拌12h。将所得中间产品水洗3次，硝酸铵的醇溶液(8g硝酸铵溶于400mL无水乙醇)洗涤3次。把0.2g CNT@SiO2分散于40mL去离子水中，超声分散均匀。在低速搅拌下加入2mL氨水(质量分数25-28％)，向上述液体中滴加1.2mL浓度为0.1M的硝酸铜，搅拌均匀。把上述悬浊液放入水热釜中于140℃下加热12小时。自然冷却后多次离心洗涤产品。在80℃下干燥完全。将0.5g Cu/C-yCuSiO3材料超声分散于125mL溶剂中。向上述溶液中加0.2g的硝酸铜，搅拌均匀后于60℃下进行旋蒸。彻底蒸干溶剂后再在氮气或氩气保护下进行焙烧。0.16g of cetyltrimethylammonium bromide (CTAB), 30mL of deionized water, 100mL of absolute ethanol, and 2mL of ammonia water with a mass fraction of 25-28wt% were mixed and stirred uniformly at room temperature. While vigorously stirring, 0.1 g of carbon nanotubes CNTs (DI=20-40 nm) was added, followed by ultrasonic dispersion for 480 min. An alcohol solution of ethyl orthosilicate (0.6 mL TEOS dissolved in 20 mL absolute ethanol) was added dropwise to the above suspension, and the vigorous stirring was continued at room temperature for 12 h. The obtained intermediate product was washed 3 times with water, and the alcoholic solution of ammonium nitrate (8 g of ammonium nitrate dissolved in 400 mL of absolute ethanol) was washed 3 times. Disperse 0.2g CNT@SiO2 in 40mL deionized water, and disperse evenly by ultrasonic. Add 2 mL of ammonia water (mass fraction 25-28%) under low-speed stirring, add 1.2 mL of copper nitrate with a concentration of 0.1 M dropwise into the above liquid, and stir evenly. Put the above suspension into a hydrothermal kettle and heat at 140°C for 12 hours. After natural cooling, the product was washed several times by centrifugation. Complete drying at 80°C. Ultrasonic dispersion of 0.5 g of Cu/C-yCuSiO material in 125 mL of solvent. Add 0.2 g of copper nitrate to the above solution, stir evenly, and carry out rotary evaporation at 60° C. Evaporate the solvent completely and then bake under the protection of nitrogen or argon.
实施例2Example 2
本实施例是在实施例1的基础上改变原料配比。This embodiment is to change the ratio of raw materials on the basis of embodiment 1.
0.16g十六烷基三甲基溴化铵(CTAB)、30mL去离子水、100mL无水乙醇、2mL 质量分数25-28wt％的氨水混合后在室温下搅拌均匀。剧烈搅拌的同时加入0.1g碳纳米管 CNTs(DI＝20-40nm)，然后进行480min的超声分散。向上述悬浊液中滴加正硅酸乙酯的醇溶液(0.9mL TEOS溶于20mL无水乙醇)，继续在室温下剧烈搅拌12小时。将所得中间产品水洗3次，硝酸铵的醇溶液(8g硝酸铵溶于400mL无水乙醇)洗涤3次。把0.2g CNT@SiO2分散于40mL去离子水中，超声分散均匀。在低速搅拌下加入3mL氨水(质量分数25-28％)，向上述液体中滴加1.8mL浓度为0.1M的硝酸铜，搅拌均匀。把上述悬浊液放入水热釜中于140℃下加热12h。自然冷却后多次离心洗涤产品。在80℃下干燥完全。将0.5g Cu/C-yCuSiO3材料超声分散于125mL溶剂中。向上述溶液中加0.2g的硝酸铜，搅拌均匀后于60℃下进行旋蒸。彻底蒸干溶剂后再在氮气或氩气保护下进行焙烧。0.16g of cetyltrimethylammonium bromide (CTAB), 30mL of deionized water, 100mL of absolute ethanol, and 2mL of ammonia water with a mass fraction of 25-28wt% were mixed and stirred uniformly at room temperature. While vigorously stirring, 0.1 g of carbon nanotubes CNTs (DI=20-40 nm) was added, followed by ultrasonic dispersion for 480 min. An alcohol solution of ethyl orthosilicate (0.9 mL TEOS dissolved in 20 mL absolute ethanol) was added dropwise to the above suspension, and the vigorous stirring was continued at room temperature for 12 hours. The obtained intermediate product was washed 3 times with water, and the alcoholic solution of ammonium nitrate (8 g of ammonium nitrate dissolved in 400 mL of absolute ethanol) was washed 3 times. Disperse 0.2g CNT@SiO2 in 40mL deionized water, and disperse evenly by ultrasonic. Add 3 mL of ammonia water (25-28% by mass) under low-speed stirring, add 1.8 mL of copper nitrate with a concentration of 0.1 M dropwise into the above liquid, and stir evenly. Put the above suspension into a hydrothermal kettle and heat at 140°C for 12h. After natural cooling, the product was washed several times by centrifugation. Complete drying at 80°C. Ultrasonic dispersion of 0.5 g of Cu/C-yCuSiO material in 125 mL of solvent. Add 0.2 g of copper nitrate to the above solution, stir evenly, and carry out rotary evaporation at 60° C. Evaporate the solvent completely and then bake under the protection of nitrogen or argon.
实施例3Example 3
本实施例是在实施例1的基础上改变负载的活性组分种类及负载量。In this example, on the basis of Example 1, the type and loading amount of the loaded active components are changed.
0.16g十六烷基三甲基溴化铵(CTAB)、30mL去离子水、100mL无水乙醇、2mL 质量分数25-28wt％的氨水混合后在室温下搅拌均匀。剧烈搅拌的同时加入0.1g碳纳米管 CNTs(DI＝20-40nm)，然后进行480min的超声分散。向上述悬浊液中滴加正硅酸乙酯的醇溶液(0.6mL TEOS溶于20mL无水乙醇)，继续在室温下剧烈搅拌12h。将所得中间产品水洗3次，硝酸铵的醇溶液(8g硝酸铵溶于400mL无水乙醇)洗涤3次。把0.2g CNT@SiO2分散于40mL去离子水中，超声分散均匀。在低速搅拌下加入2mL氨水(质量分数25-28％)，向上述液体中滴加1.2mL浓度为0.1M的硝酸铜，搅拌均匀。把上述悬浊液放入水热釜中于140℃下加热12小时。自然冷却后多次离心洗涤产品。在80℃下干燥完全。将0.5g Cu/C-yCuSiO3材料超声分散于125mL溶剂中。向上述溶液中加0.6g的硝酸铜，搅拌均匀后于60℃下进行旋蒸。彻底蒸干溶剂后再在氮气或氩气保护下进行焙烧。0.16g of cetyltrimethylammonium bromide (CTAB), 30mL of deionized water, 100mL of absolute ethanol, and 2mL of ammonia water with a mass fraction of 25-28wt% were mixed and stirred uniformly at room temperature. While vigorously stirring, 0.1 g of carbon nanotubes CNTs (DI=20-40 nm) was added, followed by ultrasonic dispersion for 480 min. An alcohol solution of ethyl orthosilicate (0.6 mL TEOS dissolved in 20 mL absolute ethanol) was added dropwise to the above suspension, and the vigorous stirring was continued at room temperature for 12 h. The obtained intermediate product was washed 3 times with water, and the alcoholic solution of ammonium nitrate (8 g of ammonium nitrate dissolved in 400 mL of absolute ethanol) was washed 3 times. Disperse 0.2g CNT@SiO2 in 40mL deionized water, and disperse evenly by ultrasonic. Add 2 mL of ammonia water (mass fraction 25-28%) under low-speed stirring, add 1.2 mL of copper nitrate with a concentration of 0.1 M dropwise into the above liquid, and stir evenly. Put the above suspension into a hydrothermal kettle and heat at 140°C for 12 hours. After natural cooling, the product was washed several times by centrifugation. Complete drying at 80°C. Ultrasonic dispersion of 0.5 g of Cu/C-yCuSiO material in 125 mL of solvent. Add 0.6 g of copper nitrate to the above solution, stir evenly, and carry out rotary evaporation at 60° C. Evaporate the solvent completely and then bake under the protection of nitrogen or argon.
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