Interaction of thionocarbamate and thiourea collectors with sulphide minerals: a flotation and adsorption study

The ability of O-isopropyl-N-ethyl thionocarbamate (IPETC), O-isobutyl-N-ethoxycarbonyl thionocarbamate (IBECTC) and butyl ethoxycarbonyl thiourea (BECTU) collectors to increase the flotation of the sulphide minerals, chalcopyrite, galena and pyrite, has been studied. For each collector, the flotation characteristics of these minerals, flotation rate constant and flotation recovery maximum, have been calculated from the flotation data and compared as a function of pH and collector concentration. Overall, the flotation performance of these collectors is stronger for chalcopyrite than for galena and pyrite. Flotation increases with collector concentration and decreasing pH values. For chalcopyrite, the collector performances of BECTU are slightly better than those of IPETC but far superior to those of IBECTC, especially at high pH values or at low collector concentrations. The flotation performance of these collectors has been shown to be in good agreement with the amount of collector adsorbed at the mineral surface. The affinity of BECTU for the various minerals has been calculated using a multilayer adsorption model.     

含稀土磷矿石捕收剂研究进展

文章在介绍当前含稀土磷矿石综合利用现状的基础上,总结了近年来国内外含稀土磷矿浮选捕收剂的研究进展,并指出了今后含稀土磷矿石捕收剂的研发趋势。     

The action of neutral oleic acid in the flotation of hematite

Acidification of solutions of oleate salts forms emulsions of oleic acid. It was found that these emulsions produce a different adsorption behaviour on different size fractions of the same mineral. At low oleate concentrations, for the finer fractions, adsorption at acid pH was higher than chemisorption at pH = 7.5; adsorption was lower for the coarser, flotation-size fractions. Therefore, the conclusions obtained in acid solutions for the adsorption of oleate on fine minerals cannot be applied to flotation-size minerals.At low oleate concentrations there is a good correlation between oleate adsorption and hematite flotation. This does not hold for oleate concentrations > 5· 10^?5M, where there is poor flotability in the acid region, although the adsorption of oleic acid is very high. This is attributed to the disordered character of the layer of cooperatively adsorbed oleic acid.     

Simultaneous inner- and outer-sphere arsenate adsorption on corundum and hematite

The ability to predict the fate and transport of arsenic in aquatic environments, its impact on water quality and human health, and the performance and cost-effectiveness of water treatment systems relies on understanding how it interacts with solid surfaces. In situ resonant surface X-ray scattering measurements of arsenate adsorption at pH 5 in 0.01 M NaCl on corundum and hematite (012) surfaces demonstrate that arsenate surface complexation is unexpectedly bimodal, adsorbing simultaneously as inner- and outer-sphere species. In addition, this bimodal behavior is found to be independent of the total arsenate solution concentration, and thus surface coverage, over the range of 10⁻⁶ to 10⁻³ M. Alternative mechanisms to produce the observed As distributions, such as arsenate dimerization or surface precipitation of an aluminum or ferric arsenate, are inconsistent with the experimentally-determined total and As-specific density profiles. Based on the location of the outer-sphere arsenate in relation to the surfaces studied, possible binding mechanisms include electrostatic attraction, hydrogen bonding to surface oxygen functional group, and configurational stabilization by interfacial water. Although the observation of outer-sphere arsenate surface complexes on a metal oxide surface is unprecedented, it is unclear if such species were absent in previous molecular-scale studies, as it is difficult for methods commonly used to investigate the mechanisms of arsenate adsorption to conclusively identify or rule out the presence of outer-sphere species when inner-sphere species are also present.     

5-alkylsalicylaldoximes as collectors in flotation of sphalerite,smithsonite and dolomite in a Hallimond tube

Flotation tests for sphalerite, smithsonite and dolomite were carried out in a Hallimond tube at various pH values and two concentrations of collector.Adsorption of 5-alkylsalicylaldoximes on the surface of minerals was examined and isotherms for 5-butylsalicylaldoxime plotted.It was shown that sorption intensity of 5-alkylsalicylaldoximes on the surface of minerals decreased in the order: smithsonite, sphalerite and dolomite.Relationship between length of aliphatic chain and collecting activity of 5-alkylsalicylaldoximes was investigated in microflotation tests in a Hallimond tube.5-Propylsalicylaldoxime proved to have the best selectivity in flotation for the range of parameters studied, taking the difference in flotation rates of smithsonite and dolomite as a criterion.It was found that modifications of pH value resulted in changes in both adsorption and flotation.     

A study of a plug-flow model for flotation froth behaviour

The importance of the cleaning action of the froth has been recognised. In order to observe the effect of various mechanisms on the gradients of mineral concentration in the froth, experiments were performed in a flotation cell using a deep froth phase where transverse motion of the froth was reduced to a minimum. The variables chosen for study include gas rate, baffling of the froth and product removal rate. The mineral studied comprised a mixed Cu, Zn and Fe sulphide with a siliceous gangue. A model based on counter-current plug-flow assumptions is advanced to describe some of the effects observed. A number of these effects are simulated using this model, leading to a better understanding of some of the processes occurring in the froth.     

Aluminous hematite: A mössbauer study

Aluminous hematites prepared in three different ways have been examined at 300K and 4.2K using the Mössbauer technique. The results indicate significant differences between the behaviour of aluminous hematites that have been subjected to high temperatures (>600° C) and those which have not. The magnitude of the room temperature quadrupole splitting of the former increases with aluminium content, approaching at ～16 mole percent substitution the value (?0.22 mm/s) exhibited by all of the low temperature specimens. This variation may be explained qualitatively in terms of a preferential c-axis contraction of the lattice upon incorporation of aluminium, which does not occur unless a c-axis defect structure is removed by subjection of the hematite to high temperatures. The solid solubility limits of high and low temperature hematites (～15 mol % and ≥19 mol % respectively) also differ, as do the room temperature decreases in hyperfine splitting (?0.82 kOe/mol % Al and ?0.86 kOe/mol % Al). At 4.2 K only low temperature hematite exhibits a decrease in hyperfine splitting with increasing Al content (?0.40 kOe/mol % Al). The absolute values of the recoil free fractions of hydrothermally prepared aluminous hematites have been determined at 4.2 K (0.70±0.02 — pure hematite, 0.82±0.02, 14±2 mol % Al substitution) and exhibit a similar increase with Al content to that previously observed for aluminous goethites. The room temperature recoil free fraction of pure hematite has been measured to be 0.64±0.02. The effects of particle size on both hyperfine splitting and recoil free fraction have been investigated.     

The surface chemistry and flotation of scheelite,II. Flotation “collectors”

The mechanism of flotation of calcium tungstate with non-complexing ionic surfactants has been examined. With fatty-acids, precipitation of the calcium soap sets in at very low concentrations. None of the conventional reagents alone provides sufficient selectivity to permit separation of scheelite from calcite.As an example of a possible chelating collector for tungstate minerals, 4-tertiary butyl catechol (4 TBC) was examined. Although such reagents are, indeed, adsorbed and induce floatability, they are useless as collectors, for several reasons. For example, 4TBC was found (unexpectedly) to be more strongly adsorbed by calcite than by scheelite; furthermore, soluble tungsten complexes were also formed.     

Surface stabilization of organics on hematite by conversion from terminal to bridging adsorption structures

Insight into the complexation of organic molecules on hematite surfaces was obtained from molecular-level studies of a simple probe molecule (methanol) with the R-cut surface of hematite. The R-cut crystal orientation of hematite, designated in this paper as α-Fe₂O₃(012), has two stable surface structures under ultrahigh vacuum (UHV) conditions based on low-energy electron diffraction (LEED) measurements. These are a (1×1) structure consisting of a bulk terminated arrangement of undercoordinated Fe³⁺ and O²⁻ surface sites and a (2×1) reconstructed structure with unknown atomic structure. Whereas the (1×1) surface is essentially free of Fe²⁺, the (2×1) surface possesses a high surface concentration of Fe²⁺ sites based on electronic structure measurements using electron energy loss spectroscopy (EELS). Methanol adsorbs dissociatively on the (1×1) surface by coordination of the molecule’s oxygen atom at a Fe³⁺ site followed by transfer of the alcohol proton to a bridging O²⁻ surface site, resulting in terminal OCH₃ and bridging OH groups. Most of the dissociated methanol molecules recombine during heating and desorb in vacuum as methanol at 365 and 415 K for the (1×1) and (2×1) surfaces, respectively. However, a significant amount of the terminal OCH₃ and bridging OH groups interchange as the surface is heated above room temperature (RT), resulting in bridging OCH₃ and terminal OH groups. The bridging OCH₃ groups are retained on the surface to higher temperature than the terminal OCH₃ groups, but eventually decompose at about 550 K via a disproportionation reaction that forms gaseous CH₃OH and H₂CO. As a result of the disproportionation reaction, some surface Fe³⁺ sites are reduced to Fe²⁺ sites. The exchange process competes more successfully with recombinative desorption of methanol (from reaction of terminal OCH₃ and bridging OH groups) on the (2×1) surface, despite the fact that this surface is already partially reduced, because terminal OCH₃ groups are more stable on this surface than on the (1×1) surface. Based on these molecular-level findings, extensive exchange terminal organic ligands and bridging OH groups may play a significant role in stabilizing organics on hematite mineral surfaces. Such exchange processes may also play a role in destabilizing hematite surfaces toward reductive dissolution.     

A study on the optimization of the arrangement of flotation circuits

The optimum utilization of available plant capacity has been investigated by simulation of a three-stage flotation circuit. By using simple models of the flotation process a wide variety of cell arrangements has been investigated and the findings tested against a number of operating flotation plants. It is concluded that the efficiency of operation of flotation systems is rather insensitive to circuit arrangement unless the circuit becomes grossly unbalanced. Circuit performance is much more sensitive to the flotation conditions and selectivity in the banks and it is only if a new circuit configuration leads to significantly improved flotation conditions that real improvements are likely. Simulation studies would require detailed modelling of such effects to be useful for circuit optimization studies.     

Species interaction in flotation: A laboratory-scale semi-batch study

Semi-batch flotation tests were performed using different narrow size fractions of three different xanthate-conditioned sulphides floated singly and together in all possible combinations. To ensure proper selective flotation conditions a gangue mineral was included in all tests. Within the reproducibility of the experimentation no significant interaction among the mineral species is indicated, a result which has useful implications in distributed rate coefficient models of flotation kinetics.The conditions under which the present findings may be valid in industrial flotation are discussed, and suggestions are made for further work.     

Two-stage reverse flotation process for removal of carbonates and silicates from phosphate ore using anionic and cationic collectors

Phosphate rock contains various gangue minerals including silicates and carbonates which need to be reduced in content in order to meet the requirements of the phosphate industry. Froth flotation has become an integral part of phosphate concentration process. In this study, double reverse flotation was applied to recover apatite from phosphate ore. H₃PO₄ and CaO were used as phosphate depressants, in acidic and alkaline conditions. Fatty acids and amines were added as carbonate and silicate collectors respectively. An experimental protocol devised to optimize the grade and recovery of phosphate using anionic–cationic method was found effective. Consequently, a required high quality of phosphate concentrate containing 30.1% P₂O₅ was obtained, with a recovery of 94%. X-ray diffraction and optical microscopy studies were performed to define the main minerals.     

赤铁矿高温原位X射线衍射研究

在空气和真空条件下对α-Fe_2O_3粉末进行了从室温到1 000℃的高温原位X射线衍射研究,分别修正了空气和真空条件下赤铁矿在27~1 000℃范围内的晶胞参数,从而得到了晶胞参数随温度变化的关系和赤铁矿在空气和真空条件下的热膨胀系数,并得出了热膨胀系数与温度的关系,即赤铁矿的热膨胀系数不随温度变化。赤铁矿在空气气氛下的热膨胀系数为αa=9.603 16×10~(-6)/℃,αc=6.647 67×10~(-6)/℃,β=2.606 33/℃;真空气氛下的热膨胀系数为αa=9.006 79×10~(-6)/℃,αc=6.891 23×10~(-6)/℃,β=2.511 51/℃。     

低品位氧化铅矿硫化浮选的影响因素研究

随着硫化铅矿资源的不断消耗,难处理氧化铅矿石己成为生产铅的重要来源.本文对产自缅甸的低品位氧化铅矿(Pb1.78％,氧化率为76.97％,铅矿物主要为白铅矿,少量铅矾和方铅矿)采用硫化-黄药浮选法,分析了硫化剂、捕收剂及抑制剂对氧化铅矿的作用机理,研究了磨矿细度、浮选药剂制度及流程等因素对浮选指标的影响.结果表明,采用1次粗选2次扫选和3次精选闭路流程,以硫化钠为硫化剂,水玻璃、六偏磷酸钠和羧甲基纤维素(CMC)为抑制剂,丁基黄药和羟肟酸为组合捕收剂,最终获得含Pb品位56.73％,Pb回收率82.83％的铅精矿.     

硫化铜镍矿浮选尾矿应用重-浮选联合流程的试验研究与生产实践

本文重点介绍了重选-浮选联合工艺对硫化镍浮选尾矿进一步处理,对其中有价金属回收的验研究与生产实践中所取得的技术成果,为资源的回收与利用上提供了一条有效的途径。     

坡缕石粘土对有机染料的吸附热力学研究

将甘肃靖远坡缕石粘土分离提纯,通过静态吸附实验,研究了坡缕石对水中有机染料亚甲基蓝、结晶紫和苯胺蓝的吸附等温线,探讨了吸附热力学特征.实验结果显示,在实验温度范围内3种染料在坡缕石上的吸附在30 min可达平衡,吸附等温线均能较好符合Langmuir模型,饱和吸附量大小顺序为:结晶紫＞亚甲基蓝＞苯胺蓝;吸附均为吸热过程,亚甲基蓝、结晶紫和苯胺蓝的吸附焓分别为15.52、9.26和2.59 kJ/mol;吸附Gibbs函数约为-35～-30 kJ/mol,吸附熵均大于零,吸附是自发过程.     

工业膨胀蛭石对水体中磷的去除研究

研究了工业膨胀蛭石对模拟养殖废水中磷酸盐的吸附性能,考察了pH值、吸附时间、固液比对吸附效果的影响,并通过原子吸收光谱法测定了蛭石在对磷酸盐吸附过程中主要金属元素的浸出含量,探究膨胀蛭石吸附水中磷的吸附平衡,对吸附机理进行了探讨。结果表明,工业膨胀蛭石对磷酸盐的吸附量可达2.76 mg/g,pH值在3~9的范围内有较高的吸附量;K、Ca、Mg这3种元素的浸出含量随着溶液中磷酸盐浓度升高而增加,Fe、Al元素则相应减少;工业膨胀蛭石对磷的吸附机理主要是先通过离子交换作用交换出层间阳离子,然后与H2PO-4、HPO2-4反应形成沉淀被吸附;吸附等温曲线均符合Freundlich公式与Langmuir公式,相关系数分别为0.978 1和0.985 1。     

蒙脱石/胡敏酸复合体对重金属离子吸附实验研究

主要研究了蒙脱石吸附胡敏酸后形成的复合体对Cu2 、Cd2 、Cr3 3种重金属离子的吸附.实验结果表明:用胡敏酸对蒙脱石改性后能提高其对3种重金属离子的吸附性能,胡敏酸浓度越大,吸附性能提高程度越大,3种重金属离子的Langmuir吸附等温线线性相关都能达到0.99以上.蒙脱石/胡敏酸复合体对3种重金属离子的吸附量都随pH值的升高而增加,随离子强度的增加而减小.另外还对其吸附动力学进行了研究,发现可用Elovicb方程和双常数方程对吸附过程进行较好地拟合.     

云南某微细粒辉钼矿工艺矿物学与浮选回收技术研究

针对云南某单一的低品位硫化钼矿,辉钼矿嵌布粒度粗细极不均匀,微细粒含量高的特点,进行了工艺矿物学与浮选回收技术研究.采用原矿粗磨—钼粗精矿再磨的阶段磨浮选矿回收工艺,以水玻璃和硫化钠做脉石矿物的抑制剂,以煤油和2#油分别作辉钼矿的捕收剂和起泡剂,对原矿Mo品位0.22％,全流程浮选闭路试验获得了钼精矿含M050.12％,回收率92.73％的浮选指标,浮选回收工艺流程合理、药剂制度简单环保.