Research, development, and application of amorphous nickel alloy catalysts prepared by melt-quenching

Raney Ni is one of the most widely used catalysts in the petrochemical industry. This material's intrinsic catalytic activity for hydrogenation may be enhanced by transforming the crystalline Ni-based alloy into an amorphous structure via melt-quenching. The meta-stability and low specific surface area of such amorphous alloys, however, can severely restrict their catalytic applications. Our work has demonstrated that the incorporation of rare earth (RE) elements increases the crystallization temperature of an amorphous Ni catalyst by 200 K. Related experimentation has determined that the specific surface area of such catalysts is dramatically increased by two orders of magnitude following alloying with Al and subsequent caustic leaching. In addition, by introducing a third metal as a promoter, the hydrogenation selectivity, corrosion resistance and magnetism of these materials may be precisely adjusted, giving rise to a family of skeletal amorphous Ni alloy catalysts, to which we apply the trade name SRNA. Among these catalysts, the SRNA-1 catalyst is used for the hydrogenation of pharmaceutical intermediates, SRNA-2 is employed for the hydrogenation of glucose into sorbitol, SRNA-3 is effective in the adsorptive desulfurization of gasoline and diesel and SRNA-4 is used for the purification of caprolactam. In addition, the SRNA-5 catalyst is useful in the hydrogenation of benzoic acid as a partial substitute for the costly Pd/C catalyst, reducing consumption of the latter during the hydrogenation process by almost 50%.

摘要Raney Ni催化剂是石油化学工业用量最大的催化剂之一, 通过急冷技术将其晶态结构转变为非晶态结构, 能够提高加氢活性. 但非晶态合金热稳定性差、比表面积小限制了这类催化材料的工业应用. 通过加入少量稀土元素, 使非晶态 Ni 晶化温度提高200 K以上; 通过加入Al再碱抽Al, 使非晶态Ni比表面积增加100倍以上; 通过加入功能助剂调节非晶态Ni的加氢选择性、增加抗酸碱腐蚀性和磁性, 从而形成了系列非晶态Ni加氢催化剂 (商品名为 SRNA). 其中, SRNA-1 用于药物中间体加氢; SRNA-2用于葡萄糖加氢制山梨醇; SRNA-3用于汽、柴油吸附脱硫; SRNA-4用于己内酰胺加氢精制; SRNA-5 用于苯甲酸加氢中替代Pd/C催化剂, 使后者的用量减少了50%.

Graphical AbstractTransforming crystalline Raney Ni into an amorphous structure by the application of a melt-quenching technique can significantly enhance the material's catalysis of hydrogenation reactions.Figure optionsDownload as PowerPoint slide