| Arones have been widely used as final products or intermediates in the field of dyes, Pharmaceuticals, agricultural chemicals and so on, and play an important role in the national economy. Friedel-Crafts acylation is the primary method for the preparation of arones, which involves the employment of metal chlorides as the homogeneous acid catalysts. Those environmentally unfriendly catalysts have always been an issue in the long-term application in industries. Therefore, the study of developing new catalysts for the Friedel-Crafts acylation to form arones becomes important and critical. In this research, H-type zeolite molecule sieves have been employed as catalysts to synthesize three types of arones, which have very important application in industries.2-methyl-6-acylnaphthalene, the precursor of 2, 6-naphthalic acid, has been synthesized via the Friedel-Crafts acylation of P-methylnaphthalene catalyzed by AICl3 as well as HZ-1 zeolite and characterized by gas chromatography, mass spectrum and NMR techniques. Detailed studying on the effects of different zeolite molecule sieves, naphthalene ring substrates, acylating reagents and solvents on acylation has shown that the best condition is HZ-1 zeolite as catalyst, butytic anhydride as acylating reagent and no solvent involved. Under such conditions, the least side reactions have been processed. The biggish difference of melting points between 2-methyl-6-butyrylnaphthalene and 2-methyl-7-butyrylnaphthalene is propitious to the industrial separation.The influence of preparation conditions of HZ-1 zeolite such as calcined temperature and ion-exchanged times on the catalytic performance has been investigated. Besides, NH3-TPD, XRD, pyridine-IR and XRF have been employed to account for the change of SiO2/Al2O3 ratio, crystallinity and acid properties of HZ-1 zeolite which will impact the catalytic performance. The four times exchanged HZ-1 zeolite calcined at 550°C exhibited optimal catalytic capability. The reaction conditions have also been optimized by adjusting catalyst dosage, reactants ratio, reaction temperature and reaction time. Under those optimized conditions, the conversion of butytic anhydride can reach as high as 77.3% with 53.1% selectivity for 2-methyl-6-butyrylnaphthalene without side-reaction occurred. Moreover, the catalytic activity of reused HZ-1 zeolite was found to decrease distinctly and can be resumed on the whole after regeneration.The catalytic performance of modified HZ-1-4 zeolite by 2% alkaline earth metal, raremetal and transition metal oxide in the butyrylation of P-methylnaphthalene has also been studied and the decrease of conversion and increase of selectivity were observed. Take both yield and cost into account, HZ-1-4 zeolite without modifiability should be chosen as the suitable catalyst in the Friedel-Crafts butyrylation of p-methylnaphthalene.In addition, benzoylation of aromatic compounds with different substituents in the presence of zeolite molecule sieves have been studied roundly. The catalytic performances of HZ-1 and HZ-2 zeolite in the benzoylation of different benzene ring as well as naphthalene ring compounds have been investigated. It has been found that the reaction activities of benzoylation are correlative with the activated degree of aromatics in the presence of zeolite molecule sieves, which correspond to the electrophilic aromatic substitution law.Several economically valuable benzophenones have been synthesized with higher yield by optimizing the benzoylation conditions of the different aromatics. HZ-1-4 zeolite has exhibited good catalytic performance in all the above benzoylation reactions. The yield of objective products 4-methoxylbenzophenone, 4-methylbenzophenone, 2-benzoylnaphthalene, 4-chlorobenzophenone and benzophenone can reach 93.8%, 94.8%, 86.0%, 76.0% and 58.0%, respectively, which are all higher than those in literatures.Magnified experiments of the benzoylation of toluene under the optimized reaction conditions have also been conducted for 4-methylbenzophenone over HZ-1-4 zeolite. Both catalyst and toluene can be recycled in such simple craft, and the distilled yield of 4-methylbenzophenone can reach 92.3% with a purity of 97.5% and good shape and colour. The total separated yield and purity of refined product are 80.7% and 100%, respectively, which come to the level of AICl3 craft at the present time. The estimation of input wastage, output, cost and profit during the craft has been conducted and indicate a good industrial prospect.Last but not least, a one-step method for the preparation of 2-methylanthraquinone and anthraquinone has been explored by employing phthalic anhydride, toluene and benzene as starting materials and HMS zeolite molecule sieve as catalyst in a liquid-solid phase batch reaction condition. It is found that HMS zeolite has good catalytic performance in such a solvent-free reaction condition. The apparent yields of 2-methylanthraquinone and anthraquinone can reach 50% and 41%, respectively, so far. And at the same time, only a little unclosed-ring acylating products are found in the product mixture.
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