A preparation process of 2-methylnaphthalene(2-MN) was proposed by isomerization, side-stream distillation and extractive distillation. The isomerization of alkyl naphthalene was catalyzed by acid-treated HBEA zeolites,and the 2-MN selectivity of isomerization was 92.70%. Side-stream distillation and extractive distillation were investigated by simulation, and effects of operation parameters on 2-MN were studied. Further, the simulated results were verified by experiment. Under the optimal condition, the mass fraction of 2-MN reached to98.09% in the product, and the yield was 83.84% in refining process. The preparation of 2-methylnaphthalene (2-MN) was proposed by isomerization, side-stream distillation and extractive distillation. The isomerization of alkyl naphthalene was catalyzed by acid-treated HBEA zeolites, and the 2-MN selectivity of isomerization was 92.70% Side-stream distillation and extractive distillation were investigated by simulation, and effects of operation parameters on 2-MN were studied. Further, the simulated results were verified by experiments. Under the optimal condition, the mass fraction of 2-MN reached to 98. 09% in the product, and the yield was 83.84% in refining process.