1-己烯羰基合成制庚醛

Synthesis of Heptaldehyde by Hydroformylation of 1-Hexene

以高压反应釜为间歇合成装置,采用乙酰丙酮二羰基铑催化剂和三苯基膦配体(PPh3)催化体系,以1-己烯与合成气为反应原料,经羰基合成制备正庚醛。通过改变反应温度、压力、铑金属质量分数、PPh3质量分数、CO/H2比,考察上述工艺条件对羰基合成反应的影响。结果表明:适当提高反应温度、铑金属质量分数,有利于提高反应转化率;适当降低反应压力或降低CO/H2,可提高醛的选择性。结合1-己烯转化率、产物醛选择性及正异比等评价指标,综合考虑,确定1-己烯羰基合成制庚醛的最佳合成工艺条件为:反应温度105℃,反应压力2.0MPa,CO/H2比1.1,铑金属质量分数200μg·g-1,PPh3质量分数12%。在上述条件下,1-己烯的转化率为95.47%,正庚醛的选择性为85.24%,产物醛的正异比为6.1。

Taking a high-pressure reactor as a batch synthesis device,by acetylacetonatodicarbonyl rhodium rhodium catalyst and triphenylphosphine ligand(PPh3)catalyst system,n-heptanal was synthesized from 1-hexene and synthesis gas via carbonyl synthesis.By changing the reaction temperature,pressure,rhodium metal concentration,PPh3 content and CO/H2 ratio,the effect of above process conditions on the carbonyl synthesis reaction was investigated.The results showed that appropriately increasing the reaction temperature and the rhodium metal concentration was conducive to increasing the reaction conversion rate;appropriately reducing the reaction pressure or reducing CO/H2 ratio could improve the selectivity of aldehydes.Combined with the 1-hexene conversion rate,product aldehyde selectivity and ratio of n-heptanal to iso-heptanal,and other comprehensive considerations,the best process conditions for the synthesis of heptaldehyde from 1-hexene were determined as follows:the reaction temperature 105℃,the reaction pressure 2.0 MPa,the CO/H2 ratio 1.1,the rhodium metal content 200μg·g-1,PPh3 content 12%.At this time,under above conditions,the conversion of 1-hexene was 95.47%,the selectivity of n-heptanal was 85.24%,and the ratio of n-heptanal to iso-heptanal in the products was 6.1.