1,4-丁二醇是一种重要的有机化工原料，主要采用炔醛法生产。随着可降解塑料行业的发展，其需求增加。铜铋催化剂是炔醛法中的一种重要催化剂，作为生产1,4-丁二醇生产中的关键技术，我国长期以来依旧依赖进口。国内也有相关探索，尽管国产硅酸镁载体催化剂活性较高但使用中载体易溶污染产品，需要后续繁琐的脱硅步骤。α-氧化铝化学性质稳定，是一种优质载体，但国内外有关α-氧化铝载体的铜铋催化剂研究极少。为此，本文通过深入研究不同制备工艺对以氧化铝为载体的铜铋催化剂性能的影响，以开发高活性、高稳定性的氧化铝载体铜铋催化剂。首先探究制备工艺对氧化铝载体铜铋催化剂性能的影响，发现焙烧温度在T8时催化剂活性最高，在T9~T11时催化剂稳定较好。沉淀体系pH为p1时活性组分负载效果较差，但在p5时催化剂颗粒之间粘连严重。原料浓度对催化剂粒径的影响比较复杂，总体上高浓度的沉淀原料利于晶核数目增长而不利于晶体长大，载体浓度的影响则相反。较高的沉淀温度（T4）和较长的老化时间（t3）均能使得催化剂负载更加均匀。在高负载量（39%）氧化铝载体铜铋催化剂制备时，分次负载的制备方案可有效提高活性组分在载体上的负载。使用三种不同的商业氧化铝作为载体制备催化剂，探究不同氧化铝对催化剂性能的影响。研究发现，以片状氧化铝为载体制备的催化剂活性与稳定性较好，而类球形块状氧化铝载体催化剂稳定性较差。最终，实现39%负载量的国产α-氧化铝载体催化剂比进口氧化铝载体催化剂活性高，与国产硅酸镁载体催化剂活性基本相同，且稳定性较好。同时探索制备硅酸镁载体催化剂。由于硅酸镁与氧化铝表面性质的差异，使用硅酸镁载体更容易制得负载量高且稳定性较好的铜铋催化剂。能够实现39%负载量的硅酸镁载体催化剂与国产硅酸镁载体催化剂的催化活性相同，且稳定性较好。此外，尝试回收利用失活α-氧化铝载体催化剂，失活催化剂在经过处理后，利用其载体进行再次负载所得39%负载量的催化剂活性和稳定性较好。
As the demand for 1,4-butanediol rises with the development of the degradable plastics industry, the production of this crucial organic chemical raw material relies heavily on the acetylenic aldehyde method. The CuO-Bi2O3 catalyst plays a pivotal role in this process. Historically, we have heavily depended on imported catalysts, and there has also been some explorations in China. Although domestic catalysts with a magnesium silicate carrier exhibit high activitym, however, this carrier's solubility poses challenges, leading to product contamination and subsequent laborious desiliconization steps. In contrast, α-Al2O3 boasts stable chemical properties, making it an excellent carrier option. Yet, there has been minimal domestic research on CuO-Bi2O3 catalysts supported by α-Al2O3 carriers. Thus, this article delves into a comprehensive examination of various preparation processes' impacts on CuO-Bi2O3 catalyst performance when using α-α-Al2O3 as the carrier. The aim is to develop α-Al2O3-supported CuO-Bi2O3 catalysts with high activity and stability.To begin with, we delved into how the preparation process affects the performance of the α-Al2O3 supported CuO-Bi2O3 catalyst. Our findings revealed that the catalyst exhibits peak activity at a calcination temperature of T8, while maintaining stability within the range of T9 toT11. A low pH (p1) in the precipitation system results in poor loading of the active components, whereas a high pH (p5) leads to severe bonding of the catalysts. The impact of varying concentrations of different raw materials on catalyst particle size is rather intricate. In general, a higher concentration of precipitation raw materials promotes the growth of crystal nuclei but inhibits crystal growth. Conversely, carrier concentration has the opposite effect. Furthermore, elevating the precipitation temperature to T4 and extending the aging time to t3 contributes to a more uniform particle distribution of the catalyst. When crafting high-loading (39%) α-Al2O3 supported CuO-Bi2O3 catalysts, a divided loading approach proves effective in boosting the loading of active components on the carrier.We prepared catalysts using three distinct commercial aluminas as carriers to investigate their impact on catalyst performance. Our studies revealed that catalysts prepared with flake alumina as the carrier exhibited better activity and stability, whereas those with spheroidal α-Al2O3 demonstrated poorer stability. Ultimately, a catalyst with a 39% loading on domestically produced α-Al2O3 exhibited higher activity compared to catalysts with imported α-Al2O3 carrier, similar activity to those with domestically produced magnesium silicate carrier, and better stability.Simultaneously, the preparation of magnesium silicate carrier catalysts was explored. Due to the differences in surface properties between magnesium silicate and alumina, it is more feasible to utilize magnesium silicate carriers for producing copper-bismuth catalysts with high loading and excellent stability. Catalysts with a 39% loading on magnesium silicate exhibited the same catalytic activity and better stability compared to domestically produced magnesium silicate carrier catalysts.Furthermore, efforts were made to recycle deactivated α-Al2O3-supported catalysts. Upon treatment of the deactivated catalyst, the carrier is reused for reloading, resulting in catalysts with a 39% loading demonstrating excellent activity and stability.
