A catalyst containing silica and an acid phase comprising sulphuric acid and HB(HSO.sub.4).sub.4, the silica having been impregnated with said acid phase and said catalyst being such that it consists essentially of particles with an average diameter of 0.1 to 150 .mu.m, the silica, prior to its impregnation with said acid phase, has a total porous volume of 1.5 to 6 cm.sup.3 per gram, said acid phase contains 0.4% to 68.8% of HB(HSO.sub.4).sub.4 and 31.2% to 99.6% of H.sub.2 SO.sub.4, and said acid phase not containing sulphuric anhydride or boric acid.