2-丁烯氢甲酰化铑/双亚膦酸酯均相催化剂的萃取除酸实验与工业侧线评价

Acid removal extraction experiment and industrial side-stream evaluation of 2-butene hydroformylation catalyzed homogenously by Rh/diphosphite ester

开展了工业装置铑/双亚膦酸酯均相催化剂萃取除酸实验,并基于萃取除酸实验确定了工业侧线评价试验工艺流程,针对中海油炼油化工科学研究院开发的铑/新型双亚膦酸酯均相催化剂进行了工业侧线评价。以Na_(2)HPO_(4)为缓冲溶液对工业装置铑/双亚膦酸酯均相催化剂萃取进行除酸实验得到的优化条件为:停留时间40~60 min,油水比(体积比,下同)4~5;以去离子水脱除引入杂质Na^(+)的萃取条件为:停留时间大于20 min,油水比6~7。在新型双亚膦酸酯配体和铑/新型双亚膦酸酯均相催化剂工业侧线评价试验中,配体含量和铑催化剂含量分别保持在(900±300) mg/kg和(195±55) mg/kg时,侧线装置运行平稳,戊醛收率为85.1%,戊醛产物正异比(物质的量之比)高于15.0。工业侧线评价试验结果表明,铑/新型双亚膦酸酯均相催化剂可达到工业装置使用要求,为铑/新型双亚膦酸酯均相催化剂工业替代试验提供了实验依据。

An acid removal extraction experiment with homogenous catalyst Rh/diphosphate ester was carried out in an industrial unit. And the industrial side-stream test of homogeneous catalyst Rh/new diphosphate ester developed by CNOOC was evaluated based on the acid removal extraction experiment. The optimum conditions for acid removal extraction of the homogenous catalyst with Na_(2)HPO_(4)as buffer solution are as follows: residence time 40-60 min, oil-water ratio(volume ratio, same below) 4-5. The extraction conditions for the removal of impurity Na^(+)by deionized water are as follows: residence time > 20 min, oil-water ratio 6-7.In the industrial side-stream evaluation experiments of new bisphosphonate ligand and Rh/new diphosphate ester homogeneous catalyst, when the content of diphosphate and Rh catalyst is kept at(900 ± 300) mg/kg and(195 ± 55) mg/kg respectively, the side-stream unit ran smoothly, the yield of valeraldehyde is 85.1%, and the mole ratio of n-valeraldehyde to iso-valeraldehyde is higher than 15.0. The results of industrial side-stream evaluation show that homogenous catalyst Rh/diphosphate ester can meet the requirements of industrial equipment, and provides experimental basis for industrial substitution experiment of homogenous catalyst Rh/diphosphate ester.