Heterogeneous Catalytic Synthesis Of Quinoline Derivatives By Amine/Acetal Catalyzed By Solid Acid

Quinoline and its ramifications are a class of significant aza-heterocyclic compounds widely used in medicine,pesticide and chemical industry,and exist in various natural and synthetic substances.A large part of the catalysts used in the synthesis of quinoline are hydrochloric acid,sulfuric acid,perchloric acid,hydrofluoric acid and other liquid acids,which lead to the increase of reaction cost and environmental pollution.It is found that solid acid is a catalyst with high activity,high selectivity,good stability and low price.In this thesis,the prepared MCM-41ordered mesoporous material and Hβmolecular sieve are used as catalysts,and the catalysts are immobilized by ionic liquids or metal modified,and the prepared catalysts are used to catalyze the synthesis of quinoline and its derivatives.The optimal reaction conditions were obtained under the determination of the combined instrument.In addition,the solid acid catalyst was tested and studied through a series of physical characterizations,and the service life and stability of the catalyst were tested.The main contents include the following aspects:（1）Gemini sulfonic ionic liquid was prepared with 2,2’-bipyridine and 1,4-butane sulfonic acid as raw materials,and MCM-41 ordered mesoporous material was prepared with cetylpyridine ammonium chloride,ammonia and tetraethoxysilane.The catalyst was characterized by XRD,XPS,FT-IR,SEM,TEM and other characterization techniques.The results showed that the disulfonic liquid was successfully immobilized on MCM-41,and the ordered mesoporous properties of MCM-41 were well preserved.The prepared catalyst was used to catalyze the synthesis of quinoline from aniline and acrolein diethyl alcohol,and tested its catalytic activity,stability and maximum yield of reaction conditions.The results indicated that the maximum yield of quinoline reached 73.7%when the reaction temperature was 120℃and the reaction time was 20h,compared with the imidazole-type mono-sulfonic acid ionic liquid prepared by the same method.The relative activity remained at 95%after several times of use,indicating good stability.（2）To buy theβzeolite as raw material,using the ion exchange method to prepare Hβzeolite,and using the deposition precipitation method to load Zn on Hβmolecular sieve,named Zn/Hβ.The catalyst was characterized by XRD,XPS,FT-IR,SEM,TEM and other characterization techniques.The results indicated that Zn of Hβsurface was fully disperse and could effectively regulate the acid site concentration of the catalyst.In addition,Zn loading did not affect the structural characteristics of the molecular sieve,and the influence on the surface of the molecular sieve was negligible.Synthesis of quinoline from aniline and acrolein diethyl alcohol using Zn/Hβas catalyst in gas phase was studied.Tested the catalytic activity,service life,regeneration property and effect of reaction conditions.The results indicated that under the temperature of maximum yield=440℃,molar ratio of aniline to acrolein diethyl alcohol 3:1,mixture LHSV=1.0h^-1 and water LHSV=1.0h^-1,the total quinoline yield of Zn/Hβcatalyst could reach about 75%and quinoline yield could reach more than 51%,far exceeding that of Hβcatalyst.The service life of the catalyst decreases with the increase of reaction time.The total quinoline yield is about 25%and quinoline yield is about 20%at the reaction time of 12h.After calcination at 550℃for 4h in air,the catalytic activity of Zn/Hβcatalyst can be almost completely recovered,indicating that the deactivation of Zn/Hβcatalyst is reversible and has excellent regeneration performance.