SU825138A1 - Method of preparing catalyst for liquid-phase oxidation of tetralin and phenanthrene - Google Patents

Description

(54) METHOD FOR PREPARING THE CATALYST

FOR TYTHRALINE HEAT-PHASE OXIDATION

OR PENANTRENA. The above objective is achieved by a method for preparing a catalyst, comprising reacting a polymer, in which polyurethane of the general formula C-0- (CHi) -NH-CO-ln is used. where p 4-8, with an inorganic salt of cobalt, which is used as anhydrous cobalt chloride, in an environment of chloroform. The catalyst is prepared as follows. Example 1-. A polyurethane of the formula (: 0- (cH2) -NH-CO {I, where p 4, in an amount of 10 g is placed in 125 ml of chloroform and 15 g of anhydrous CoClt salt obtained by calcining CoCl2H O at 200 ° C. Is added. 8 hours at room temperature. After that, the cobalt-containing polymer is separated from the unreacted CoClt salt by decantation. The cobalt content in the catalyst is 29.8%. 5 g of the obtained catalyst. c is carried out at 90 ° C, the air supply rate is 2.7 l / min After 240 minutes since the start of oxidation, the yield of tetralone - 1 is 21.3 wt.%, tetralol - 1 - 1.76 wt./about. Yaryle /) 2. A polyurethane of the formula -O- (CH-NH-CO-, i, where item 6, in an amount of 10 g is placed in 125 ml of chloroform and 14 g of anhydrous salt of CoCI is added. The mixture is stirred for 8 hours at room temperature temperatures (e. After which the cobalt-containing polymer is separated from the unreacted salt of CoClj. by decantation. The cobalt content of the catalyst is 25.0 / v. The catalyst obtained is tested during the liquid phase oxidation of tetralin. 100 ml of tetralin and 0.5 g of the obtained catalyst are loaded into a bubble apparatus with a stirrer. The process is conducted at 30 ° C, the air supply rate of 2.7 l / min. After 270 minutes from the start of the oxidation, the yield of tetralone-1 is 17.5 w / v, tetralol - 1 - 2.2 wt.%. Example 3. The catalyst was prepared as in Example 2, with the difference that 100 ml of chloroform was used and 14.5 g of anhydrous CoClg was added ;. The resulting catalyst contains cobalt in the amount of 25.0%. The catalyst obtained is tested during the liquid phase oxidation of tetralin. 100 ml of tetralin and 0.5 g of the obtained catalyst are loaded into a bubbling apparatus with a bashman. The process is carried out at 90 ° C, an air flow rate of 2.7 l / min. The results of the analysis on the yield of tetralone-1 and tetralol-1 are given in table. 1. Table. Vacuum distillation of the oxidate with a residual pressure of 1 mm Hg. Art. after 240 minutes from the start of the reaction, B shows that during oxidation, 29.19% by weight of tetralone - 1 and 5.78% by weight of by-products are formed. The amount of unreacted tetralin is 65.01 wt.%. Example 4. The catalyst is prepared as in Example 3, with the only difference that chloroform is used in an amount of 125 ml. The resulting catalyst contains cobalt in the amount of 25.0%. The catalyst is tested during the liquid phase oxidation of tetralin. In a bubbling apparatus with a stirrer, 100 ml of tetralin and 0.5 g of the obtained catalyst, temperatures of 100 ° C, air flow rate of 2.7 l / min are loaded. The results of the analysis on the yield of tetralone-1 and tetralol-1 are given in table. 2. Table 2 Example 5. The catalyst was prepared in the same manner as in example 2, with the only difference that polyurethane with p 8 was used, chloroform was used in an amount of 75.0 ml, and the mixture was stirred for 7 hours. with a cobalt content of 20.5%. The catalyst is tested during the liquid phase oxidation of tetralin. 100 ml of tetralin and 0.01 g of the obtained catalyst are loaded into a 100-ml bubble apparatus. Temperature 140 ° С, air supply speed 2.7 l / min. After 160 minutes from the start of the oxidation, the yield of tetralone-1 is 5.88% by weight, tetralol is 1 0.17% by weight.

Example 6 A catalyst was prepared in the same manner as in Example 2.

The catalyst obtained is tested during the liquid phase oxidation of phenanthrene. The oxidation is carried out at 125 ° C. The catalyst is used in an amount of 1.0 g; o-dichlorobenzene is used as the solvent. The process is carried out in the presence of 10 vol. / about valeric acid. The volume of the reaction mixture is 100 ml.

The results of the experiments are given in table. 3

Table 3

90.9

0.04015

0.004 92.9

0.1181 0.009 93.9

0.2253 0.015 0.017 95.3

0.3461 90.4 0.022

0.4178 91.8 O, 032

0.3562

Thus, the catalyst obtained by the inventive method has a high activity — the yield of the target product reaches 83%, while no mixed and resinous products are formed in the mixture.

Claims (2)

1.Kotl Revsky, I.P., et al. Synthesis and catalytic properties of copper-containing organic polymers. Sat Catalysts containing deposited complexes. Novosibirsk, 1977. p. 207. 2. Efendiyev. A. A. et al. Catalytic properties of cobalt complexes with a polymer sorbent in the reaction of liquid-phase oxidation of o-xylene. Sat Catalysts containing applied complexes. Novosibirsk, 1977, p. 211 (prototype).