The monometallic catalytic membrane reactors were established with catalytic hollow fibers prepared by supporting the polymer-anchored monometallic palladium catalyst (PVP-Pd, EC-Pd or AR-Pd) on the inside wall of CA or PSF hollow fibers. PVP=poly(N-vinyl-2-pyrrolidone), EC=ethyl cellulose, AR=melamine-formaldehyde resin, CA=Cellulose acetate, PSF=polysulfone. The selective hydrogenation of butadiene in crude 1-butene was carried out in the catalytic membrane reactors at 40 degrees C under 0.1 MPa. Among the above catalytic hollow fibers, the catalytic activity and selectivity of the PVP-Pd/ CA monometallic hollow fiber were the best values, but there was still 2.6% 2-butene in the product. In order to inhibit the isomerization reaction of 1-butene, the bimetallic catalytic CA hollow-fiber reactors were produced and used for the above reaction. The bimetallic palladium-cobalt catalyst PVP-PdCl2-0.5Co(OAc)(2), supported on the CA hollow fibers was reduced by NH2NH2 or NaBH4. A remarkable synergic effect of palladium and cobalt reduced by NaBH4 was observed.