Physical and thermal treatment of phosphate ores — An overview

The annual consumption of phosphate rock approached 150 million tons. The marketable phosphate is usually 30% P₂O₅ or higher. The run-of-mine material is mostly of lower grade which needs processing or upgrading. The processing techniques of phosphate ores depend mostly on the type of associated gangue minerals present in the mined rock. In some cases, simple, inexpensive techniques are enough to produce the required grade. For example, crushing and screening is used to get rid of the coarse hard siliceous material, and attrition scrubbing and desliming is used to remove the clayey fine fraction. If silica is the main gangue material, single-stage or double-stage flotation is the conventional mineral processing technique used in this case. If the ore is igneous carbonatitic alkaline or ultra basic phosphate deposit, crushing, grinding, scrubbing, and flotation associated with other steps such as magnetic and/or gravity separation is proved to be successful in upgrading this type of ore. The sedimentary phosphate ores having carbonate-apatite as the main phosphate minerals and containing carbonates (calcite and/or dolomite) represent a challenge in the field of phosphate concentration due to similarity in the physico-chemical properties of surfaces of the ore constituents. Also, if considerable amount of organic matter constitutes the main gangue material, upgrading of the ore becomes difficult. New flotation systems (techniques and reagents) are being developed to treat these challenging phosphate ores. Furthermore, calcination is another solution for upgrading these difficult-to-treat types of ores. However, calcination is indicted with some controversial drawbacks. This overview discusses and summarizes the State-of-the-Art and the existing efforts to overcome these problems and to produce a high-grade phosphate product suitable for fertilizers and other phosphate compounds.     

Evaluation of digital image processing (DIP) in analysis of magnetic separation fractions from Na-feldspar ore

Combination of flotation and magnetic separation methods is widely used for enrichment of feldspar ores by purifying from dark-colored gangue minerals such as iron and titanium. In this study, the removal of dark-colored minerals from feldspar ore (Aydin Cine region of Turkey) was studied using a dry magnetic separator. The effect of several parameters such as feed particle size, blade angle, and roll speed on the removal efficiency was investigated in detail. In addition, the gangue contents of the magnetic and non-magnetic products were determined by a digital image processing (DIP) method in terms of using color differences between the feldspar sample and gangue minerals. The results obtained from this study clearly indicated that the dry magnetic separation method can be successfully applied in enrichment of feldspar. Meanwhile, the particle size of the sample showed no significant influence on the separation recovery. According to the results obtained from the digital image processing process, the sample with 0.04% cross sectional area of dark-colored minerals can be obtained at roll speed of 100 rpm and 130° of blade angle using the original particle size of 500×106 μm. Additionally, most importantly, these results showed that digital image processing method can be used to determine gangue content (dark-colored minerals) of the magnetic separation products compared to conventional methods as a simple, a reliable, and a repeatable method.     

X射线衍射-扫描电镜等技术研究秘鲁铜硫矿石选矿工艺矿物学特征

秘鲁铜硫矿石的主要回收对象是铜和硫矿物,由于铜矿物嵌布复杂、粒度过细以及与各种脉石矿物或金属矿物交生关系紧密,利用传统工艺矿物学研究方法如化学分析、光学显微镜检测等较难准确定量其工艺矿物学参数。本文采用化学分析、X射线衍射、扫描电镜、偏光显微镜及矿物参数自动分析系统(MLA)等技术手段,研究秘鲁铜硫矿石的化学成分、矿物组成和主要矿物的嵌布特征、粒度分布及单体解离特性等,并对影响选矿指标的主要矿物学因素进行分析。结果表明:矿石中主要元素为Cu(0.65%)和S(9.53%)。矿石中黄铁矿(16.57%)含量较高,形态较为规则,与其他矿物之间的交生关系相对简单,粒度普遍偏粗,其中粒径大于0.30mm的黄铁矿占95.06%。铜矿物主要以不规则粒状、皮壳状、网脉状、纤维状、尘粒状、斑点状分布于脉石中或与黄铁矿、闪锌矿、磁铁矿等金属矿物交生紧密,粒度极不均匀,使得铜矿物解离难度加大,且矿石中云母(12.51%)、绿泥石(3.74%)、滑石(3.34%)、高岭石、蒙脱石(3.59%)等黏土质矿物含量较高,在磨矿过程中易发生泥化从而恶化分选环境。根据该类型矿石的工艺矿物学特性,本文建议采用"粗磨-部分优先浮铜-铜硫混浮-混合精矿再磨再选分离"的工艺流程,可得到质量高的铜、硫精矿。     

Magnetic properties of the Bled El Hadba phosphate-bearing formation (Djebel Onk,Algeria): Consequences of the enrichment of the phosphate ore deposit

To improve the enrichment of the Thanetian marine phosphate ore deposit from the quarry of Bled El Hadba (Djebel Onk, Algeria) before its exploitation, we first conducted a joint study using different techniques for comparison. These studies reveal that magnetic minerals play a significant role within the matrix of the central productive unit which is squeezed between two other units. Magnetic separation procedures show that there are some positive correlations between magnetic susceptibility and grain size fraction (80–250 μm). These dolomite-rich fractions are more clearly separated. Different tools were used to characterize the magnetic minerals (X-ray, microprobe, differential scanning calorimetry, thermogravimetric and thermomagnetic analyses). They show correlations between magnetic phases and the presence of associated magnetic minerals within the matrix or included in the phosphate ore deposit. They enabled us to distinguish a series of magnetic minerals (magnetite, hematite, maghemite, goethite, ilmenite, pyrite, iron–titanium oxide and titanium oxide sulphate) and to determine that Fe and Ti are prevalent in the separated fractions, following the same variation as Mg. The phosphorous (phosphate) rate is higher in the non-magnetic material, especially in the layers that are rich in dolomitic carbonates (upper and lower units), which could be trapped within the dolomitic matrix, while Magnesium (dolomite) is more important in the magnetic fraction. The separation of phosphate elements and dolomite carbonates is effective and therefore the ore can be enriched through magnetic procedures. Comparison between products enriched by magnetic separation, flotation and calcination showed important differences, chemically, economically and technically speaking.     

湖北省南漳县红星磷矿磷块岩特征与物质组分研究

湖北省南漳县震旦系沉积型红星磷矿矿体P_2O_5平均含量23.91%,矿石自然类型主要为角砾状磷块岩,其次为白云质磷块岩、泥质纹层状和条带状致密块状磷块岩。工业类型主要为钙(镁)质和硅钙(镁)质磷矿,其次为硅质磷矿。矿石矿物为胶状磷灰石和微晶磷灰石,经x-射线衍射物相分析,其种属为含碳氟磷灰石。嵌布粒度以细-中粒为主。脉石矿物主要为白云石、伊利石、高岭石、铁质。经测定当磷块岩磨矿粒度小于0.1mm,其磷酸盐矿物单体解离率可达92.53％,这为确定合理的选矿流程具有实际意义。     

The Comprehensive Utilization and Purified Research on Kaolin Ores in Huichang

Kaolin ores in Huichang contains these minerals of quartz sand, kaolin, mica and feldspars. In order to recover these valuable resources, some experiments of screening, classification, magnetic separation, grinding and flotation are carried out on the basis of the kaolin ore properties. The test results indicate that quartz sand concentrate can be directly obtained when vibrating screen size used is 10 meshes. Materials that are smaller than the screen hole are injected to hydraulic cyclones which controlling classification size is 325 meshes; kaolin concentrate containing above 33.70% Al2O3 and 0.37% Fe2O3 can be well beneficiated from the overflow through magnetic separation with one stage rougher and cleaner to remove iron. On the other hand, the hydrocyclone spigot flow to grinding and flotation with one stage rougher and two scavengers, mica and feldspars concentrate can be beneficiated in sequence. Therefore, these valuable minerals of kaolin ores can be realized comprehensive utilization.     

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.     

Selective flotation of scheelite from calcium minerals with sodium oleate as a collector and phosphates as modifiers. II. The mechanism of the interaction between phosphate modifiers and minerals

The respective effects of phosphate modifiers on the solubility of calcium minerals in water, on the surface charge of the minerals and on the adsorption of the phosphates and of sodium oleate on the mineral surface were examined. The Auger spectra and the infrared spectra of the minerals treated with these reagents were also investigated. The ability of the phosphates to complex metal ions was determined by nephelometric titration. The structures of the minerals and their effects on their floatability, as well as structures of the phosphates and their effects on the complexation power were discussed. A mechanism of depression of the calcium minerals through the selective complexing dissolution of calcium ions from the mineral surface was derived and explains the higher selectivity obtained in scheelite flotation when (NaPO₃)₆ or Na₄P₂O₇ are used as modifiers.     

Electrokinetic properties and flotation behaviour of apatite and calcite in the presence of sodium oleate and sodium metasilicate

Calcite is generally associated with apatite minerals in phosphate deposits. To explore the possibility of separating these minerals by a soap flotation technique, their electrokinetic properties and flotation behaviour were studied in the presence of sodium oleate.Microelectrophoresis data indicate oleate adsorption on these minerals, and from Hallimond-tube flotation tests it has been noted that in a controlled pH environment and for a certain sodium oleate concentration range, separation of these minerals is possible.The study of apatite/calcite-sodium metasilicate-sodium oleate systems indicates the preferential adsorption of silicate at the calcite surface. This suggests the potential use of sodium metasilicate as the modifying agent for the separation of apatite from calcite by depressing calcite when using sodium oleate as collector.     

Flotation of calcareous Mussorie phosphate ore

Separation of Mussorie rock phosphate (P₂O₅ = 20%) from Uttar Pradesh, India, containing pyrite, calcite and other carbonaceous impurities by flotation has been successfully attempted to upgrade the phosphate values. Based on Hallimond cell flotation results of single and synthetic mineral mixtures of calcite and apatite using oleic acid and potassium phosphate, conditions were obtained for the separation of calcite from apatite which is considered to be the most difficult step in the beneficiation of calcareous phosphates. Further studies using 250 g of the mineral (?60 +150 and ?150 mesh fractions, deslimed) in laboratory size Fagergren subaeration machine employed a stagewise flotation viz. carbonaceous materials using terpineol, pyrite using potassium-ethyl xanthate and calcite using oleic acid respectively. Separation was, however, found to be unsatisfactory in the absence of a depressant.Among starch, hydrofluosilicic acid and dipotassium hydrogen phosphate, which were tried as depressants for apatite in the final flotation stage, dipotassium hydrogen phosphate proved to be superior to others. However, the tests with the above fractions did not yield the required grade. This was possibly due to insufficient liberation of the phosphate mineral from the ore body and different experimental conditions due to scale up operations. Experiments conducted using ?200 mesh deslimed fractions has yielded an acceptable grade of 27.6% P₂O₅ with a recovery of about 60%. The results have been explained in terms of the specific adsorption characteristics of phosphate ions on apatite and the liberation size of the mineral.     

Effects of an ultrasonic field on the flotation selectivity of barite from a barite-fluorite-quartz ore

The influence of an ultrasonic field frequency of 22 kHz and intensity of 0.5 W/cm² has been examined on the flotation of barite, fluorite and quartz as well as on their ability to adsorb dodecyl- and cetylsulphates. The tests affected the flotation of pure minerals in a Hallimond tube as well as the flotation of a natural barite-fluorite ore. It has been found that ultrasonic pretreatment of minerals causes an increase in the flotation rate of barite and a decrease in the flotation rate of fluorite. Ultrasonic pretreatment of the natural barite-fluorite ore before its flotation is the most advantageous. In this case it is possible to obtain concentrates of barite composed of a low amount of CaF₂. This may be explained by the different effects of ultrasonic vibrations on barite and fluorite which cause some improvement of the selectivity of their flotation separation.For a full explanation of these results the effects of ultrasonic pretreatment of the minerals on their adsorption properties and surface topography have been investigated, as well as the direct influence of ultrasound on the adsorption process.     

用浮选法分离萤石的探讨

本文简略地叙述了萤石的物理特性及共生矿物组合。根据萤石的物理化学性质,选择了对萤石的分选方法,并着重分析了用重选和浮选法分离萤石的技术方案比较,确认用浮选法分离萤石是有效的方法之一,因而对用浮选法分离萤石进行了一系列的不同药剂种类和用量试验,并选择了对萤石富集比较有效的药剂对某铁矿中微细萤石的浮选富集和提纯,结果采用粗选与精选相结合的提纯流程,可以达到预想的目的,萤石的纯度可达97%左右。     

Oolitic ores in the Bakchar iron-ore cluster (Tomsk Oblast)

Oolitic iron ores are typified, and their morphology and composition are studied. Special attention is focused on the character of distribution of valuable and harmful admixtures and determination of the principal minerals concentrating these elements. As a result of this study, three types of ores are identified, such as “loose” ores, cemented ores with glauconite–chlorite–clay cement, and well-cemented ores with siderite cement. The morphology and composition of the ore oolites are characterized. The forms of occurrence of calcium phosphates (anapaite) and phosphates of rare-earth elements (monazite, cularite) that are related to the harmful phosphorus admixture are described. According to the analysis of the elemental composition, the fractions of (–1…+0.2) and (–1…+0.1) mm in the western and eastern segments, respectively, may be promising for processing.     

The flotation of niccolite — A single mineral study

High arsenic levels in nickel sulphide concentrates can often present technical and environmental problems at the smelter. In some ores a flotation separation between the nickel sulphides and the arsenide minerals is required in order to meet smelter specifications for arsenic. There is very little information in the literature about such separations and the flotability of nickel arsenides in general. Data are presented here from a single mineral flotation investigation into the flotability of niccolite (NiAs), one of the key nickel arsenide minerals present in nickel sulphide ores in Australia.Niccolite is only weakly flotable with xanthate collector at pH 9 and this behavior is independent of the grinding environment. This suggests that high arsenic levels in nickel concentrates are not due to niccolite flotation, but are more likely to be due to flotation of more floatable arsenic-bearing minerals such as gersdorffite. Cyanide diminishes the poor recovery of niccolite further.     

Effect of oxidation potential and zinc sulphate on the separation of chalcopyrite from pyrite

The effects of oxidation potential (Eh) and zinc sulphate on the separation of chalcopyrite from pyrite were investigated at pH 9.0. The flotation recovery of these minerals is Eh dependent with maximum separation obtained at 275 mV SHE. Zinc sulphate addition improved this mineral separation at an Eh value of 275 mV by selectively depressing pyrite flotation. A different result was obtained at lower Eh values where zinc sulphate addition improved chalcopyrite flotation but had no or little effect on pyrite flotation. These opposite effects of zinc sulphate on mineral flotation were reconciled by examining the surface species of these minerals. The selective depression of pyrite flotation by zinc sulphate was also confirmed in the flotation of two copper ores.     

粉石英与红柱石的浮选分离机理研究

本文以油酸钠作为捕收剂,研究了磷酸氢二钠、柠檬酸和硅酸钠等抑制剂对粉石英与红柱石浮选分离效果的影响.结果表明,磷酸氢二钠是红柱石与粉石英浮选分离的一种优良的抑制剂;在其最佳浓度0.47×10-2 mol /L,浮选液pH值为8.5时,粉石英与红柱石浮选回收率差高达47.86％.红外光谱及Zeta电位分析结果表明,油酸钠对红柱石兼有物理和化学吸附作用,对粉石英仅有物理吸附作用,因而对红柱石有更强的捕收能力;磷酸氢二钠对粉石英表面起解吸作用,能有效抑制粉石英起浮,从而实现粉石英与红柱石的分离.     

安徽马钢凹山铁矿断层带中粘土矿物质组分的研究

对马钢凹山铁矿区断层带中规模较大的粘土矿,采用化学分析、岩矿鉴定、Ｘ衍射分析、红外吸收光谱分析、差热分析、透射电镜及物理工艺性能等综合分析测试方法进行了研究,查明其岩石、矿石类型及６种类型矿石的物质组分和矿物特征、２组矿石样品的物理工艺性能,在此基础上,从选矿和提高矿石质量等方面提出了意见     

粤北下庄铀矿田中铀酰矿物的成分特征——对核废料处置库中UO2氧化行为的启示

下庄铀矿为一花岗岩型铀矿，矿田地处湿热气候条件下，沥青铀矿普遍产于破碎带中，这种特定的产出环境致使该区沥青铀矿经受了强烈的风化，形成种类繁多、数量丰富的铀酰矿物；而我国高放废物地质处置库拟建在花岗岩体中。因此，下庄铀矿田是开展核废料氧化的天然类比研究的理想地区，并对我国的高放废物地质处置库的安全性评价有重要的指导作用。下庄铀矿田的铀酰矿物组合为铀酰氢氧化物、铀酰硅酸盐和铀酰磷酸盐，包括柱铀矿、黄钙铀矿、calciouranoite、红铀矿、富硅铀酰相、硅钙铀矿、钙铀云母和盈江铀矿等。根据它们的空间分布特征可划分成两个风化系列，即硅酸盐风化系列和磷酸盐风化系列，其共生次序分别为：沥青铀矿→铀酰氢氧化物（氧化物）→富硅铀酰相→硅钙铀矿和沥青铀矿→铀酰氢氧化物（氧化物）→钙铀云母→盈江铀矿。在该矿田中，铀酰氢氧化物是亚稳定相矿物，常常被铀酰硅酸盐或磷酸盐取代，因此，铀酰氢氧化物仅出现在少数样品中，而铀酰硅酸盐和铀酰磷酸盐矿物则非常普遍。矿田中的铀酰矿物在化学成分上以富钙为其显著特征，由于核废料地质处置库近场地下水中的Ca^2＋含量应该明显比下庄矿田地下水中的高，因此，我们预测含Ca的铀酰硅酸盐和铀酰磷酸盐矿物等热力学上的稳定物相很可能是地质处置系统中最主要的铀酰矿物，处置库内放射性核素的迁移主要是由这些矿物控制的。     

云南斑岩型多金属金矿的嵌布特征及赋存状态研究

云南西部有大量低品位金矿资源,且具有嵌布粒度不均匀、矿石结构复杂、解离不完全等特点,传统工艺矿物学分析不易快速、准确测定金赋存状态及载金矿物的嵌布特征。本文利用矿物自动分析系统(MLA)、化学分析等方法对滇西多金属金矿进行系统的工艺矿物学研究,查明了该矿的矿物组成、嵌布粒度、连生及包裹关系,同时阐明了载金矿物的工艺矿物学性质对金回收率的影响。结果表明:金主要以游离态自然金的形式存在,嵌布粒度极细,主要集中在0.01~0.02 mm粒度级别;小于0.074 mm粒级的金占原矿总金量的50.08%,其余金以微细包裹体分散于黄铁矿、磁铁矿、黄铜矿等载金矿物中。但载金矿物粒度较细,解离性差,嵌布不均匀,因此提高载金矿物解离度是提高金回收率的一个重要参考方向。