Ceramic ultrafiltration membranes were used to separate titanium silicalite-1 (TS-1) catalysts from the slurry of catalytic ammoximation of cyclohexanone to oxime. Silica was shown to have a great effect on membrane fouling in the alkaline environment of this system. In the ammoximation system, there are three main silica sources, which are residual silica on the catalyst particles surface during preparation, silica dissolved from TS-1 catalyst particles by ammonia solvent, and silica sol added into the reaction slurry to inhibit the dissolution erosion of the TS-1 catalyst. The silica dissolved by ammonia has been proved to influence membrane fouling most among the three silica sources. This was because the amount of silica dissolved by ammonia was the largest, and the polymerization of silica monomers at high concentration caused colloid particles formation, which led to a dense cake layer depositing on the membrane surface. Meanwhile, the size reduction of catalyst particles caused by alkaline dissolution also increased specific resistances of cake layers.