The residues of salt lake brine from which potassium had been removed were used to extract Rb＋ and Cs＋ together with a sulphonated kerosene（SK） solution of 1.0 mol/L 4-tert-butyl-2-（α-methylbenzyl） phenol（t-BAMBP）. Rb＋ and Cs＋ were enriched and separated effectively by precipitating Mg2＋ before extraction and by scrubbing out K＋ and Na＋ repeatedly before stripping. The effects of the volume ratio of organic phase to aqueous extraction phase（O/A）, alkalinity of aqueous phase（c（OH）-）, interference from K＋ and Mg2＋, and ratio the volume of organic phase to aqueous scrubbing phase（O/A′） were investigated. The experimental brine was extracted optimally by 5-stage extraction with 1.0 mol/L t-BAMBP in SK, c（OH-）=1 mol/L, and O/A=1：1. The scrubbing yield of rubidium was only about 10.5% when the extraction solvent was washed 3 times with 1×10-4 mol/L Na OH at O/A′=1：0.5. After 5-stage countercurrent extraction, the final extraction yields of Rb＋ and Cs＋ reached 95.04% and 99.80%, respectively.
A series of iron（III） chlorophyllins was prepared from silkworm excrement crude chlorophyll extract as a raw material. Aerobic oxidation of cyclohexene by using the prepared iron（III） chlorophyllins as biomimetic catalysts was studied under atmospheric pressure in the absence of reducing agent and solvent. The results indicate that chloro- phyll iron porphyrins have better catalytic performance than the industrial-applied iron tetraphenylporphyrin and cobalt tetraphenylporphyrin, and possess a higher selectivity for 2-cyclohexen-1-one. The smaller the polarity of iron（III） chlorophyllin＇s ligand is, the easier the catalytic oxidation of cyclohexene will be. Esterification products of iron（III） chlo- rophyllins can catalyze the oxidation of cyclohexene better than non-esterified iron（III） chlorophyllins, and therefore show a higher conversion of cyclohexene and a higher selectivity for 2-cyclohexen-l-one than the non-esterified ones. Among the six synthesized iron（III） chlorophyllin catalysts, iron（III） methyl-pyropheophorbide-a is the best biomimetic catalyst for the highest conversion of cyclohexene. The influences of catalyst＇s substituent, polarity and ring structure on the catalytic performance were discussed. The catalytic performance of iron（III） chlorophyllins improves with decreasing polarity, increasing conjugated degree of porphyrin＇s ring or enhancing chlorophyllins＇ stability. Possible mechanism of cyclohexene aerobic oxidation catalyzed by iron（III） chlorophyllins was also discussed.
LIU Xiao-hong LI Yong-jin YANG Wei-jun GUO Can-cheng
The aerobic oxidation of p-menthane to p-menthane hydroperoxide （PMHP） in the presence of metalloporphyrins was investigated in an intermittent mode under an atmospheric pressure of air. Several important reaction parameters, such as the structure of metalloporphyrin, the air flow rate, and the temperature, were studied. The preliminary mechanism of the aerobic oxidation of p-menthane catalyzed by metalloporphyrins was also discussed. The results show that the reaction is greatly accelerated by the addition of metalloporphyrins at very low concentration, in terms of both the yield and formation rate of PMHP, and the high selectivity of PMHP is maintained during the reaction. Temperature of 120 ℃ and reaction time of around 5 h are the optimal conditions for the best result in the presence of 0.06 mmol/L monomanganeseporphyrins （（p-Cl）TPPMnC1）. Furthermore, the yield of PMHP is increased remarkably when the reaction is carried out under programmed temperature compared with the constant temperature. When the reaction is catalyzed by 0.06 mmol/L（（p-Cl）TPPMnCl） at the air flow rate of 600 mL/min and 120 ℃ for 4 h, and then the temperature is reduced to 110 ℃, for another 4 h, the yield of PMHP reaches 24.3 %, which is higher than that of the reaction at a constant temperature of 120 ℃ or 110 ℃ for 8 h.
