Hydroformylation Of Alkenes In FCC Light Gasoline Catalyzed By Rhodium-Phosphine Complexes

The new standard for gasoline in China requires a lower olefin content.Since olefins have been used as an important component to increase the octane number of gasoline in China for a long time.Catalytic cracking（FCC）gasoline will reduce the octane number of gasoline after reducing olefins.In our work,hydroformylation of olefins in FCC light gasoline catalyzed by rhodium complexes has significantly reduced the olefin content in gasoline,increased the octane number,and giving clean gasoline fuels.At the same time,the market for syngas has been broadened,resulting in low-value coal-derived syngas to high-value gasoline.Firstly,the rhodium phosphine complex as a homogeneous catalytic system was used to evaluate the activity of three catalysts in the hydroformylation of olefins from FCC light gasoline.The results showed that the homogeneous catalytic system of Rh（CO）（PPh3）（acac）and triphenyl phosphine without thiophene sulfur had good activity.The total olefins content of 44.95%of light gasoline remained 30.32%after reaction for 24 h.That is,the total olefin conversion is 38%.Secondly,Rh（CO）（PPh3）（acac）and triphenyl phosphine as the homogeneous catalytic system was used to optimize the hydroformylation process conditions.The control variable method was used to explore the best single factor process conditions,then orthogonal test was used for getting the optimal reaction conditions.The results showed that under the condition of a reaction time of 9 h,reaction temperature of103°C,reaction pressure of 2.5 MPa,phosphine-rhodium ratio of 100:1,catalyst concentration of 1.25mmol/L,stirring rate of 400 r/min and light gasoline of 25 g,total olefin conversion,the total aldehyde yield and the catalyst conversion frequency could respectively reach 65.06%,63.87%,and 956.31 h^-1.Finally,rhodium catalysts immobilized on ferromagnetic particles were prepared by chemical coprecipitation.First of all,the catalyst was characterized to provide the basis for the optimization of the catalys.Then the immobilized catalyst in the hydroformylation of olefins was found to have good activity that the total olefin conversion was 29.97%and total aldehyde yield was 29.56%.In addition,the regeneration cycle performance of the catalyst was studied.It was found that the total olefin conversion was reduced to 10.54%and the total aldehyde yield was reduced to10.38%after repeated use four times.Finally,a uniform SPION-Rh catalyst intermediate Fe3O4@DA@DPPBac with a particle size of about 4 nm was also preliminarily prepared and the preparation of the SPION-Rh catalyst was continued.