| Most of the copper-molybdenum resources in China are multi-metal complex ores, however, the existing flotation reagents and flotation processes for copper-molybdenum polymetallic complex sulphide ores often fail to achieve appropriate comprehensive recovery of resources. Therefore, it is an urgent need to research and develop new collectors and flotation processes.N,N-di-n-alkyl-N’-alkyl acylthiourea (DU) was synthesized using n-hexanoyl chloride as a raw material, and the synthesis conditions were as following:n-hexanoyl chloride:KSCN:secondary amine:PEG-400(molar ratio)=1:1.08:1.10:0.03, substitution reaction of4h, addition reaction of2h, reaction temperature of20℃. The product is a solid product with productivity of96.94%, purity of91.10%, and yield of88.31%. N-(alkoxy-propyl)-N’-benzoyl-thiourea (MU) was synthesized using benzoyl chloride as a raw material, and the synthesis conditions were as following:benzoyl chloride:KSCN:amine:PEG-400(molar ratio)=1:1.50:1.10:0.03, substitution reaction of1h, addition reactions of1h, the reaction temperature of20. The product is a solid product with productivity of80.13%, its was purity83.28%, and the yield was76.73%. UV absorption spectroscopy, infrared spectroscopy,1H NMR and I3C NMR were taken to characterize the acylthiourea products. UV spectra and infrared spectroscopy means were performed to investigate the interaction of acylthiourea and metal ions; the effect of pH, initial concentration of acylthiourea on the adsorption of acylthiourea on the surface of chalcopyrite with different size fractions were studied with UV spectroscopy analysis. According to flotation without collectors, or with neutral oil and non-polar ion collectors, the flotation behaviors and performance of copper-molybdenum ores were investigated based on Pearson hard and soft acid-base theory, quantum chemistry, molecular orbital theory and with infrared spectroscopy, interfacial chemical performance parameters, contact angle, surface energy and interface action analyses. Base on the results of flotation process and agent studies, compound collector CSU-300was invented, using DU and MU as raw materials.The flotation results of Dexing porphyry copper-molybdenum ore showed that Cu-Mo rougher concentrate containing15.32%Cu,0.294%Mo, recovers of Cu83.23%and Mo79.43%was achieved under the condition of rougher grinding fineness-0.074mm65%, roughing lime dosage1000g/t (pH=9.0), the amount of the CSU-300collector64g/t. The concentration result of the Cu-Mo of Dexing Cu-Mo ore indicated that the separation process with sodium sulfide is better than the bank one which can get the Cu-Mo rough concentrate with the index of1.221%Mo,25.92%Cu, the recovery of Mo83.85%,enrichment ratio142. The sodium sulfide cleaning separation process of Cu-Mo not only can improve the beneficiation index of Mo sharply, but also the beneficiation index of Cu and Au are both better than mixing flotation or partly mixing flotation. Compared to mixing flotation or flash flotation, Mo recovery rate was enhanced23.68%,14.72%respectively and enrichment ratio raised3.3to2.8times. The recovery of Cu increased1.56%,2.5%respectively, Au3.11%,3.96%. The industrial tests of flotability ranking flotation of Mo indicated that under the condition of0.381%Cu, Mo0.0064%of Dexing mine, the Mo concentrate could be achieved with Mo0.655%, Cu25.47%, Mo enrichment ratio101.72, the recovery of Mo77.06%. A section total recovery of copper was87.56%, sulfur76.35%. Comparing with the same period in grinding section1#, system0-1#, the flotation indexes of copper, sulfur, gold both have been improved; Comparing with flotation indexes of Mo in grinding section2#and3#of the same period, Mo recovery rate has raised24.35%, Mo enrichment ratio raised62.83. The Cu-Mo Separation test under the small closed-circuit experiment of Mo concentrate produced by preferential flotation of Mo process has been investigated. The result indicated that CSU-300collector used in the preferential flotation of Mo process can make Cu-Mo Separation much easier, due to higher molybdenum rougher concentrate grade and unaffected xanthate the role of other powerful collector. Under the flotation conditions of sodium sulfide18.5kg/t, sodium silicate1.2kg/t, kerosene130g/t, the technical indexes were obtained:the Mo concentrate assays48.83%, Cu0.83%, recovery of Mo90.55%; the copper concentrate assays27.08%, recovery of Cu99.96%.For copper-molybdenum mine in Duobaoshan mine in kibbled case, molybdenum, copper and other floating appropriate period of grinding fineness-0.076mm (-200mesh) accounted for about68%; the dosage of CSU-30030～40g/t;2#oil frother14g/t; lime dosage1.5kg/t; considering the influence on the flotation process mixed by mid-core, the matching relationship is CSU-300:35g/t,2oil:14g/t. The ore is floated by the bulk flotation, then concentrates copper by strengthening flotation, the indexes of Cu-Mo mixed concentrate copper grade28.77%molybdenum0.80%and recovery of the Mo90.71%are achieved as well as Cu concentrate contains15.88%Cu, the recovery of Cu9.77%under the condition of rougher grinding fineness-0.0454mm96%, the mixture collector of butyl xanthate butylamine and black drug (3:1). When copper concentrate was mixed, copper grade is26.36%, the recovery86.76%.In order to realize the separation of the Cu-Mo of Duobaoshan copper mine, the Cu-Mo mix concentrate should be re-ground and the reasonable fineness is45μm-98%. In a dosage of Na2S is1000g/t and (NaPO3)6250g/t (50×5).The Mo concentrate containing48.63%Mo,0.73%Cu, the recovery of Mo87.40%as well as C-Mo middling with18.6%C,3.31%Mo,1.30%Cu. Compared with ore, the yield of this middling is less (0.036%). The industrial test results of Duobaoshan Cu-Mo ore indicate that the Cu concentrate can be achieved with the index of Cu grade28.26%, Mo0.13%, Au8.38g/t, Ag102.52g/t and the Mo concentrate contain Cu0.78%, Mo48.55%, Ag recovery63.58%, Cu92.60%, Au78.31%and comprehensive recovery of Mo up to70.65%by under the program flowsheet and the recommended reagent system. At the same time, the C-Mo middling with C19.25%, Mo5.19%, Cu1.93%was obtained. The results of semi-industrial test with the scale of10t/d indicate that the Cu concentrate and the Mo concentrate can be achieved with the index of Cu grade24.33%, Mo0.19%, Au8.91g/t, Ag150.56g/t, Cu recovery72.79%, Au65.55%, Ag60.11%and Mo grade47.14%, Cu0.88%, Mo recovery71.52%, Mo enrichment ratio4000respectively under the program flowsheet and the recommended reagent system. At the same time, the C-Mo middling with C18.76%, Mo4.93%, Cu2.98%was obtained. |
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