Study On Preparation And Catalytic Performance Of Cu^Ⅰ/SO₄^2-/M_xO_y And Cu^Ⅰ/S₂O₈^2-/M_xO_y Catalysts

Dimethyl carbonate(DMC) is a environmental-friendly green chemistry, the synthesis route of methanol oxidative carbonylation to DMC is in accord with the concept of 21^th century green chemistry, at the same time, it is very advantageous in thermodynamics and mature in technics with cheap materials. It has been proved that the industrialized CuCl catalyst possesses the innate defect of deactive easily, serious causticity to equipment and polluting production. Asone of research focus currently, the catalysts of H zeolite loaded Cu^â… and Cu^â…¡are low active on the liguid oxidative carbonylation of methanol. Some research indicated that some amount of Br(?)nsted acid sites lies in SO₄^2-/M_xO_y and S₂O₈^2-/M_xO_y solid (super) acid, but whether can it be applied in soild ion exchange, it is still no any detailed report. In the thesis, the catalytic activity ofCu^â… /SO₄^2-/M_xO_y and Cu^â… /S₂O₈^2-/M_xO_y (M=Al, Zn, Fe) catalysts of which solid(super) acids were prepared by impregnating method were evaluated on slurry reactor, as well as solid (super) acids and catalysts were characteristic by XRD, py-FTIR, FTIR, NH₃-TPD, H₂-TPR, XPS etc. Through experiment research andanalyse, the conclusion shows as below:(1) All of the Cu^â… /SO₄^2-/M_xO_y and Cu^â… /S₂O₈^2-/M_xO_y (M=Al, Zn, Fe) catalysts with low amount of chloride showed high activation on liquid oxidative carbonylation of methanol to DMC, the catalysts (M=Al, Fe) possessed higher activation than the other(M=Zn); at the same reaction condition, all of the SO₄^2-/M_xO_y and S₂O₈^2-/M_xO_y loaded Cu^â… catalysts wereproved to be higher active than the traditional CuCl and HY zeolite loaded Cu^â… catalyst.(2) Through the characteristic of py-FTIR and element analyse of XPS surface etching, it is proved that the Br(?)nsted acid sites on solid (super) acid(M=Al, Zn, Fe) can be exchanged by metal ion, and metal ion maintains primary metal valency.(3) The XRD characteristic of solid (super) acids and catalysts shows thatthe structure of solid (super) acids has no obvious change if Cu^â… was loadedunder the rato of W_CuCl/W_carrier≤1:2, part of CuCl exchanges with solid (super)acids, and the other lies in catalyst in the form of monlayer.(4) According to the result of activation evaluation, the optimized heatingtemperature of solid (super) acids is in the range of 500～600℃. At thetemperature metal component can be loaded and exchanged with the greatest extent on solid acid.