Study On The Synthesis Of Extractant 2-Hydroxy-5-Nonylacetophenone Oxime And Its Analog's Design And Synthesis

The copper resources is abundance in china, but one third of the copper resources are low quality copper ores and copper oxide ores. After several decades exploitation the quality of copper ores were lower since reform and opening. On the contrary, the needs of copper market were increase year by year. Hydrometallurgy solved the resource contradictory problem. The hydrometallurgy can convert copper oxide ores into valuables, and it has the advantages that turnover of material is simple, the degree of recovery of metals from material is high, little environmental pollution and automation of process is easy achieved, compared with copper traditional metallurgy by fire process.The copper extractant which was studied in this paper was 2-hydroxy-5-nonylacetophenone oxime (HNAO). Its name of commodities is LIX84. There was wide application of extractant HNAO in hydrometallurgy. HNAO was synthesized from 4-nonylphenol, acetyl chloride, anhydrous aluminum chloride and hydroxylamine hydrochloride in this paper. The optimized reaction conditions were obtained through the single factor experiment. The results were as follows: (1) While preparing HNA one-pot method was employed, thus tetrachloro ethylene was selected as solvent, n(4-nonylphenol): n(acetyl chloride): n(anhydrous AlCl3) was 1: 2: 1.2, the molecular ratio of additional acetyl chloride to 4-nonylphenol was 0.2: 1 on the completion of addition of aluminum chloride, the reaction was carried out under reflux (120℃) for 6h. The yield of the HNA based on 4-nonylphenol was 78.0%. (2) While preparing HNAO the distilled HNA was used and toluene was used as solvent, sodium ethylhexanate was used as PTC, n(HNA): n(hydroxylamine): n(Na2CO3) was 1: 1.2: 0.7, the reaction was carried out under 75℃for 4.5h. The yield of the HNAO based on HNA was 97.9%. The structures of the intermediate and final product were characterized by FT-IR.In this paper HNAO's analog 5-methy-8-hydroxy-1-tetralone oxime was designed based on the design method of new extractant. The optimized reaction conditions were obtained through the single factor experiment. The results were as follows: (1) In the synthesis of 4-butyryl chloride, the reaction mixture must be dry. Compounds were stirred at 60℃for 4 hours, and then were heated to 80℃for 7 hours. The preferred ratios ofγ-butyrolactone, thionyl chloride, anhydrous ZnCl2 was 0.6: 0.76: 0.015, activation time was 1 hour, thionyl chloride was added during a period of 2 hours, the yield of 4-Chlorobutanoyl chloride based onγ-butyrolactone was 91.7%. (2) While preparing 5-methy-8-hydroxy-1-tetralone, one-pot method was employed, thus the preferred ratios of 4-methyphenol, 4-Chlorobutanoyl chloride, anhydrous AlCl3 was 1: 2: 2.2, tetrachloro ethylene was selected as solvent. The esterification temperature was 120℃and reaction time was 3h. On the completion of addition of the anhydrous AlCl3, the proper temperature and time was 75~100℃(the first 3h), 120℃(the later 2h). (3) While preparing of 5-methy-8-hydroxy-1-tetralone oxime, the preferred ratio of hydroxylamine hydrochloride, 5-methy-8-hydroxy-1-tetralone was 1.13: 1. The reaction temperature was 90℃. The structures of the target compounds were confirmed by FT-IR, 1H-NMR, 13C-NMR. The results showed that the structures of the synthesized compounds were identical with the expected ones.