Dehydration catalyst and preparation method thereof and application of dehydration catalyst in production of isobutene by dehydration of tert-butyl alcohol

[0038] [Example 1]

[0039]It is weighed 85 gaseous aluminum stone powder and 10 grams of raw cryptochrine mix, add 5 wt% dilute nitric acid solution, thoroughly stir, mix, mix the wet material to a crushing machine with a cylindrical die. Dry, intercept 1 cm small segment, placed in 8 hours in an oven at 80 ° C for 5 hours after 600 ° C, 5 hours, to obtain alumina forming body (specific surface area of ​​300m) 2 / g). The above-described molded body is placed in a stainless steel reaction kettle, and the amount of La added in an equivalent impregnation amount is 0.5% of the nitrate solution, and after 10 hours at 150 ° C, it is taken after 15 hours at 80 ° C, After stirring at 600 ° C for 3 hours, it was immersed with a phosphorus 5 wt% phosphoric acid solution for 2 hours, and then dried for 6 hours at 120 ° C for 5 hours. After 5 hours of 5 hours, the desired tert-butanol dehydrated production of high purity isobutylene catalysts The LA mass content is 0.5%, and the phosphorus mass content is 5%.

[0040] With a fixed bed reactor, the water and the tert-butanol mass ratio of 1: 1 is a raw material, and the reaction pressure is 0.05 MPa, the reaction pressure is 0.05 MPa, and the weight of tert-butanol is 2.0 h. -1 Under the reaction conditions, the results after the reaction 48h were as follows, the tert-butanol conversion was 100%, the isobutylene selectivity was 99.5%; after 1500 hours, the tert-butanol conversion was 100%, isobutylene selectivity 99.3%.

[0041] [Example 2]

[0042] It is weighing 99 grams of thin aluminum stone powder and 10 grams of rafting mixture, and 5% dilute nitric acid solution is added, stirred, mix, mix the wet material to the squeezing machine with a three-leaf-shaped die. Dry, intercept 1 cm small segment, placed in an oven at 60 ° C for 10 hours, 10 hours in a muffle furnace at 400 ° C, resulting in alumina forming profile (350m specific surface area) 2 / g). The above-described molded body is placed in a stainless steel reaction kettle, and the amount of Ce weight is 5% by the equivalent impregnation amount of 5%, and then taken out at 180 ° C for 10 hours, after 120 ° C for 6 hours, 450 After calcination at ° C for 5 hours, it was immersed in a volume of phosphoric phosphoric phosphoric acid solution for 2 hours, and then dried for 10 hours at 80 ° C, after 3 hours of 600 ° C, the desired tert-butanol dehydrated production of high purity isobutylene catalysts. The Ce mass content was 5%, and the phosphorus mass content was 1%.

[0043] With a fixed bed reactor, the water and the tert-butanol moiety of 0.2: 1 are raw materials, and the reaction pressure is 0.02 MPa, the reaction pressure is 0.02 MPa, the tert-butanol weight is 8.0 h. -1 Under the reaction conditions, the results were taken as follows, and the t-butanol conversion was 99.5%, the isobutylene selectivity was 99.9%.

[0044] [Example 3]

[0045] It is weighed 85 gaseous aluminum stone powder and 10 grams of raw cryptochrine mix, add 5 wt% dilute nitric acid solution, thoroughly stir, mix, mix the wet material to a crushing machine with a cylindrical die. Dry, cut into 1 cm small segment, placed in an oven at 80 ° C for 5 hours in a muffle furnace at 600 ° C, resulting in alumina forming body (300m specific surface area) 2 / g). The above-described molded body is placed in a stainless steel reaction kettle, and the amount of La weight is 0.5% by the equivalent impregnation amount of 0.5%. After 10 hours at 150 ° C, it is taken out, dried at 80 ° C for 15 hours, 600 After 3 hours of calcination at ° C, the desired t-butyl alcohol dehydrated catalyst was obtained, and the LA mass content was 0.5%.

[0046] With a fixed bed reactor, water and tert-butanol mass ratio of 1: 1 tert-butan alcohol aqueous solution are raw materials, at a reaction temperature of 400 ° C, reaction pressure 0.05 MPa, tert-butanol weight drop 2.0H -1 Under the reaction conditions, the results were 98.6% by the t-butanol conversion of 98.6%, and the isobutylene selectivity was 97.5%; after 500 hours, the tert-butanol conversion was 95.3%, isobutylene selectivity 92.1%.