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以膦化硅烷作桥联剂,硅胶作载体,用四种方法合成了化学键联固相化的RhCl(CO)(PPh_3)_2络合物催化剂。实验表明,以[RhCl(CO)_2]_2作原料,用先键联后络合法合成的催化荆(编号ⅡA)活性最高,在温度为110℃、压力为40kg/cm~2、合成气H_2/CO=1,液体空速(LHSV)为31/l.hr时,己烯-1醛化转化率为95.7%,庚醛选择性为100%。用ⅡA催化剂进行了温度、压力、空速和H_2/CO比等变量对上述反应活性的影响实验。并在较佳条件下(即110℃,40kg/cm~2),用己烯-1进行了205小时的寿命实验,实验过程中活性基本不下降,转化率一般在93%以上,选择性在95%以上,铑流失低于0.4ppm(液相产物中之浓度),此结果比用同系均相催化剂还好。计算了催化剂单位表面铑原子数、膦原子数以及其它表面性质,从而推导出催化剂的表面结构。
Phosphine silane as bridging agent and silica gel as carrier, four kinds of methods were used to synthesize RhCl (CO) (PPh_3) _2 complex catalyst. The experimental results showed that the catalytic activity of [RhCl (CO) _2] _2 as the starting material was the highest with the first coupling reaction and the latter with the highest catalytic activity at 110 ℃ and pressure of 40 kg / cm ~ 2. H 2 / CO = 1 and liquid hourly space velocity (LHSV) of 31 / l.hr, the conversion of hexene-1 was 95.7% and the selectivity of heptanal was 100%. The influence of temperature, pressure, space velocity and H 2 / CO ratio on the above reaction activity was investigated using ⅡA catalyst. Under the optimal conditions (ie, 110 ℃, 40kg / cm ~ 2), the life span of 205 hours was measured with hexene-1. The activity did not decrease and the conversion rate was generally above 93% Above 95% rhodium loss is less than 0.4 ppm (concentration in the liquid phase product), which is better than with homologous homogeneous catalysts. The number of rhodium atoms, the number of phosphine atoms and other surface properties on the surface of the catalyst were calculated, and the surface structure of the catalyst was deduced.