Synthesis, Characterization And Structural Modulation Of Zirconium Based Catalysts For The Synthesis Of Quinoline Derivatives

Quinoline derivatives are a kind of important fine chemical products,which have been used widely in many aspects.However,there are many problems in the synthesis of quinolines,such as equipment corrosion、complicated process and environment pollution.So it is very important to develop a new type of catalyst for the synthesis of quinoline derivatives.Based on the detailed investigation and previous work of our group,this thesis has finished the following content:Firstly,the seven catalysis were synthesized,that is:Zr（SO₄）₂/MCM-41、Zr（SO₄）₂/MCM-41（roasting at 300℃）、Zr（SO₄）₂/MCM-41（roasting at 450℃）、SO₄^2-/ZrO₂（roasting at 450℃）、SO₄^2-/ZrO₂（roasting at 650℃）、ZS/MCM-41（roasting at650℃）、ZS/P-MCM-41（roasting at 650℃）,then they were applied to be the catalysts in aniline and n-butyl aldehyde reaction in the synthesis of quinoline derivatives.The results show that the first three catalysts perform well in catalytic activity,get the main product yields remain at 45%,and they are no corrosion equipment and can be easily separated from reaction system.SO₄^2-/ZrO₂（roasting at 650℃）is a kind of solid super acid,when it was used in the synthesis of quinoline derivatives,the yields of the main product can reached to 64%,what’s more,the stability of this catalyst is excellent,the catalyst can be reused 4 times and keep quinoline yield almost invariant.The latter two kinds of catalyst were improved the stability because of the loaded onto MCM-41,and ZS/P-MCM-41（roasting at 650℃）can get 67%ethyl-2-3-propyl quinoline which is a very promising catalyst.Moreover,SO₄^2-/ZrO₂（roasting at 650℃）were characterized by BET and Py-IR after each used in reaction in order to investigate the change of structure and acid properties of catalysts,and the relationship between the catalyst structure and their product distribution were also studied.Clearly,the quantity of Lewis acid and specific surface area will reduce gradually,pore structure slightly changed.The higher specific surface area,lead to faster the reaction rate and the better catalytic activity.When the specific surface area decreased significantly,the yield of the product was reduced.Quinoline products produced by lewis acid and changes in the quantity of strong Lewis acid can produce a new product which named octane aldehyde.The Lewis acid character is the main influence factors in the synthesis of quinoline derivatives compared with the specific surface area.