Hierarchical Malachite Microsphere Catalyst in theEthynylation of Formaldehyde for 1,4-Butynediol Synthesis

The challenge of improving the wear resistance of Cu–Bi catalysts continues to persist in the industrial production of 1,4-butynediol (BYD) through the ethynylation of a formaldehyde reaction. Herein, We successfully prepared a hierarchical malachite microsphere catalyst by cooling the crystallization process under atmospheric pressure. The hierarchical malachite microspheres are uniform spheres with a diameter of 18 μm, which are composed of numerous two-dimensional microplatelets paralleling the sphere surface. The cooling rate is a crucial factor that significantly influences the development of the crystal morphologies. A slower cooling rate enhances the crystallinity of the catalyst particles, leading to the formation of larger microplatelets on the catalyst surface. Experimental results demonstrated that the spherical malachite catalyst, synthesized via the cooling crystallization method, exhibits excellent wear resistance and sustained catalytic performance in the ethynylation of formaldehyde for the synthesis of BYD.