Abstract: The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH were prepared and investigated. The synthesized catalysts were fully characterized by BET, XRD (X-ray diffraction), TPR (temperature programmed reduction), IR (infra-red adsorption), NH3-TPD (temperature programmed desorption) and CO2-TPD (temperature programmed desorption) techniques. The results showed that the surface area of catalysts decreased with increasing metal content, and the metals as well as Cu-Ni alloy co-existed on the reduced catalyst surface. There existed interaction between metal and carrier, and moreover, metal particles affected obviously the acidity and basicity of carrier. The large amount of basic sites facilitated the activation of methanol to methoxyl species and their subsequent reaction with activated carbon dioxide. The cata-lysts were evaluated in a continuous tubular fixed-bed micro-gaseous reactor and the catalyst with bimetal loading of 20% (by mass) had best catalytic activities. Under the conditions of 393 K, 1.1 MPa, 5 h and gas space velocity of 510 h−1, the selectivity and yield of DMC were higher than 86.0 % and 5.0 %, respectively.

Key words: molecular sieve, Cu-Ni bimetal catalysis, dimethyl carbonate, carbon dioxide, methanol

摘要： The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH were prepared and investigated. The synthesized catalysts were fully characterized by BET, XRD (X-ray diffraction), TPR (temperature programmed reduction), IR (infra-red adsorption), NH3-TPD (temperature programmed desorption) and CO2-TPD (temperature programmed desorption) techniques. The results showed that the surface area of catalysts decreased with increasing metal content, and the metals as well as Cu-Ni alloy co-existed on the reduced catalyst surface. There existed interaction between metal and carrier, and moreover, metal particles affected obviously the acidity and basicity of carrier. The large amount of basic sites facilitated the activation of methanol to methoxyl species and their subsequent reaction with activated carbon dioxide. The cata-lysts were evaluated in a continuous tubular fixed-bed micro-gaseous reactor and the catalyst with bimetal loading of 20% (by mass) had best catalytic activities. Under the conditions of 393 K, 1.1 MPa, 5 h and gas space velocity of 510 h−1, the selectivity and yield of DMC were higher than 86.0 % and 5.0 %, respectively.

关键词: molecular sieve, Cu-Ni bimetal catalysis, dimethyl carbonate, carbon dioxide, methanol