Preparation of high-purity fluorite and nanoscale calcium carbonate from low-grade fluorite

Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.

Anisotropic surface broken bond properties and wettability of calcite and fluorite crystals

Anisotropic surface broken bond densities of six different surfaces of calcite and three surfaces of fluorite were calculated. In terms of the calculated results, the commonly exposed surfaces of the two minerals were predicted and the relations between surface broken bonds densities and surface energies were analyzed. Then the anisotropic wettability of the commonly exposed surfaces was studied by means of contact angle measurement. The calculation results show that the （101^-4）, （213^-4）and （01 1^-8）surfaces for calcite and （111） for fluorite are the most commonly exposed surfaces and there is a good rectilinear relation between surface broken bond density and surface energy with correlation of determination （R^2） of 0.9613 and 0.9969, respectively. The anisotropic wettability of different surfaces after immersing in distilled water and sodium oleate solutions at different concentrations can be explained by anisotropic surface broken bond densities and active Ca sites densities, respectively.

Fluid-melt Inclusions in Fluorite of the Huanggangliang Skarn Iron-Tin Deposit and Their Significance to Mineralization

For the first time, fluid-melt inclusions are found in fluorite of the Huanggangliang skarn iron-tin deposit (HSID). The fluorite was formed in the main stage of mineralization, named the hydro-skarnization stage. The inclusions contain various components such as Fe, Mg and Cr from deep sources. The melts of primary inclusions are mainly Ca- and F-rich and those of secondary inclusions tend to become Si-rich. During this evolution process, the melts and iron daughter minerals decreased and even vanished. These facts reveal that the evolution of the primary mineralizing fluids and the differentiation of the fluids and melts are the main factors leading to the deposition of Fe, Sn and other elements. This discovery confirms the magmatic genesis of the HSID and has filled in the gaps in the research of magmatogenic skarn deposits and furnished new methods for such research. Furthermore, it has enlarged the scope of the research on fluid inclusions.

Effects and mechanisms of fluorite on the co-reduction of blast furnace dust and seaside titanomagnetite

The co-reduction roasting and grinding-magnetic separation of seaside titanomagnetite and blast furnace dust was investigated with and without fluorite addition at a reduction roasting temperature of 1250°C for 60 min, a grinding fineness of-43 μm accounting for 69.02 wt% of the total, and a low-intensity magnetic field strength of 151 kA/m. The mineral composition, microstructure, and state of the roasted products were analyzed, and the concentrations of CO and CO_2 were analyzed in the co-reduction roasting. Better results were achieved with a small fluorite dosage(≤4 wt%) in the process of co-reduction. In addition, F^- was found to reduce the melting point and viscosity of the slag phase because of the high content of aluminate and silicate minerals in the blast furnace dust. The low moisture content of the blast furnace dust and calcic minerals inhibited the hydrolysis of CaF_2 and the loss of F^-. Compared with the blast furnace dust from Chengdeng, the blast furnace dusts from Jiugang and Jinxin inhibited the diffusion of F-when used as reducing agents, leading to weaker effects of fluorite.

REE Geochemistry of Fluorite from the Maoniuping REE Deposit,Sichuan Province,China:Implications for the Source of Ore-forming Fluids

Fluorite is one of the main gangue minerals in the Maoniuping REE deposit, Sichuan Province, China. Fluorite with different colors occurs not only within various orebodies, but also in wallrocks of the orefield. Based on REE geochemistry, fluorite in the orefleld can be classified as the LREE-rich, LREE-flat and LREE-depleted types. The three types of fluorite formed at different stages from the same hydrothermal fluid source, with the LREE-rich fluorite forming at the relatively early stage, the LREE-flat fluorite in the middle, and the LREE-depleted fluorite at the latest stage. Various lines of evidence demonstrate that the variation of the REE contents of fluorite shows no relation to the color. The mineralization of the Maouiuping REE deposit is associated spatially and temporally with carbonatite-syenite magmatism and the ore-forming fluids are mainly derived from carbonatite and syenite melts.

Adsorption of octanohydroxamic acid at fluorite surface in presence of calcite species

The surface properties of fluorite are often affected by dissolved gangue species(e.g.,calcite)during the flotation process.Microflotation testing with and without the addition of calcite supernatant was conducted using octanohydroxamic acid(OHA)as the collector.The results revealed that dissolved calcite species significantly affected the flotation behavior of fluorite.Fourier transform infrared spectra confirmed that the decrease in flotation recovery was linked to lower OHA adsorption.Solution chemistry analysis indicated that CaCO_(3) and Ca^(2+)from the calcite supernatant were the most favorably adsorbed species,and X-ray photoelectron spectroscopy analysis confirmed the surface adsorption of calcite species.Density functional theory simulations provided a detailed analysis of the multidentate adsorption configuration of OHA,which was the most favorable for adsorption on the fluorite surface.The adsorption energy calculation showed that the calcite dissolved species were more stably adsorbed on the fluorite surface than OHA.The pre-adsorption of calcite dissolved species hindered the adsorption of OHA due to electrostatic repulsion.

Hydrothermal Sedimentary Mineralization of the Super-large Bamianshan Fluorite Deposit in Zhejiang Province, China

The Bamianshan fluorite deposit is a super-large one recently discovered in Zhejiang Province of China. This paper presents an analysis of its geological background, orebody and ore characteristics, petrochemical characteristics of host rocks, rare earth elements （REE） of rocks and ores, fluid inclusions in fluorite and Sm-Nd isotopic features in an effort to study its sedimentary mineralization. The result shows that the super-large Bamianshan fluorite deposit is of hydrothermal sedimentation genesis, deformed by the later hydrothermal fluid. Integrated with host rocks and orebody characteristics, it is inferred that the deposit originates from the Cambrian sedimentary rocks. And the later magmatic activities deformed some orebodies in different degrees, forming steeply dipping vein orebodies in the tectonic belts regionally.

Fluid Inclusion Studies and Geochemistry of Rare Earth Elements of Hydrothermal Fluorites from Pohrenk,Kirsehir,Central Turkey

Fluorite mineralization occurs along fractures and cracks of Middle Eocene and Pliocene limestones and marls in the north and northeast of the P?hrenk region (?i?ekdagi, Kirsehir). Tb/Ca – Tb/La and Y/Ho ratios were obtained from REE contents of fluorites which have revealed that mineralization is of hydrothermal type. Negative Ce anomalies and positive Eu anomalies reflect that hydrothermal solutions once had high oxygen fugacity. Fluid inclusion studies indicate that homogenization temperatures of mineralization varied between 90°C and 200°C, and hydrothermal solutions are composed of NaCl + KCl + MgCl2 + H2O. In addition, salinity measurements show that hydrothermal solutions were mixed with meteoric or rock formation water. Geologic setting, REE geochemistry and fluid inclusion studies suggest that mineralization was deposited from a solution generated by mixing of magmatic and meteoric water under epithermal conditions.

Recent advances and perspectives of fluorite and perovskite-based dual-ion conducting solid oxide fuel cells

High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.

EFFECTS OF DISSOLVED MINERAL SPECIES ON THE SURFACE CHEMICAL CHARACTERISTIC,ELECTROKINETIC PROPERTY AND FLOTATION BEHAVIOR OF FLUORITE AND SCHEELITE

Interactions between the dissolved mineral species and other mineralsurface were investigated using solution chemistry calculation, -potential measurement, AES analysis and flotation tests. It has been indicated that there canbe precipitation of scheelite over fluorite in scheelite supernatant at PH> 4.The conversion of fluorite into scheellte was detected by AES. Fluorite in the supernatant of scheelite exhibits nearly identical electrokinetic property andflotation behavior with those of scheelite. The selective flotatlon separation of fluorite from scheelite or vice vasa may be achieved by using selective amphoteric collector for fluorite at PH<4 to avoid surface conversion.

Fluorite deposits in China:Geological features,metallogenic regularity,and research progress

Fluorite is one of the important mineral raw materials in the industry.In China,it is mainly distributed in the provinces and regions such as Hunan,Zhejiang,Jiangxi,Inner Mongolia,Fujian,and Henan provinces,boasting huge reserves and large numbers of deposits.However,most of the fluorite deposits are on a small or medium scale.The main fluorite deposits in China were studied in this paper.Their geological features and metallogenic regularity were summarized and compared.Meanwhile,based on their main genetic factors including metallogenic fluid sources and main metallogenic geological processes,they were divided into two groups,namely meso-epithermal deposits and magmatic-hydrothermal deposits.Furthermore,based on the prospecting achievements and research progress obtained in fluorite deposits in recent years,prospecting potential predictions were made for the metallogenic prospect areas and major prospecting areas of fluorite in China.This aims to provide a theoretical basis and direction for future fluorite prospecting in China.

A New Classification Scheme of Fluorite Deposits

Fluorite deposits occur in a variety of geologic environments throughout the globe. It may occur as the main or only economically recoverable ore mineral in deposits or may present as the accessory gangue minerals with other ores. It is therefore necessary to understand various genetic types of the fluorite deposit. The present paper synthesises the information of some of the known fluorite mineralisation from the world so that an understanding of them can help in establishing reliable criteria for further search of fluorite deposit. On the basis of a combination of geological background information and fluorite geochemistry, a new classification scheme is proposed.

Characteristics of rare-earth elements (REE),strontium and neodymium isotopes in hydrothermal fluorites from the Bailashui tin deposit in the Furong ore field,southern Hunan Province,China

In this paper the authors present the REE concentrations and Sr and Nd isotopic compositions of fluorites from the Bailashui tin deposit of the Furong ore field,southern Hunan Province. The results showed that the total amount of REE in fluorites is usually low,ranging from 0.705 to 8.785 μg/g with the chondrite-normalized REE dis-tribution patterns similar to those of the Qitianling granites in the study area,characterized by LREE-enrichment patterns with pronounced negative Eu anomalies. The fluorites vary in Sr isotopic composition within the range of 0.7083-0.7091,the values are lower than those of the granites and higher than those of the host carbonate rocks in this area. The εNd(t) values of fluorites vary between -9.4 and +10.3,revealing that both the crust-and mantle-source materials were involved in the ore-forming hydrothermal fluids. Combined with previous studies on this ore deposit,the Bailashui tin deposit is temporally and spatially closely related with granitic magmatism in this area. The hydro-thermal fluorites are the product of fluid/rock interactions between granitic magmatic hydrothermal fluid and marine carbonate rocks. The REE and F in the ore-forming fluid were derived from the granites,whereas Sr in the ore-forming fluid came mainly from the granitic magmatic hydrothermal fluid and marine carbonate rocks,although variations in Sr isotopic composition cannot be explained by a simple mixture of these two end-members. Evidence demonstrated that the ore-forming fluids are of crustal-mantle mixing origin,but that the fluids were probably in-completely homogenized and this may be caused by inhomogeneous mixing of the fluids of different sources.

Rare earth element(REE) geochemistry of different colored fluorites from the Baoshan Cu–Pb–Zn deposit, Southern Hunan,South China

The Baoshan Cu–Pb–Zn deposit, located in the central part of the Qin–Hang belt in South China, is closely related to the granodiorite-porphyry. However, the characteristics and the source of the ore-forming fluid are still ubiquitous. According to the crosscutting relationships between veinlets and their mineral assemblages, three stages of hydrothermal mineralization in this deposit were previously distinguished. In this contribution, two different colored fluorites from the major sulfide mineralization stage are recognized:(1) green fluorites coexisting with Pb–Zn ores;and(2) violet fluorites coexisting with pyrite ores. Y/Ho ratios verify the green fluorites and violet fluorites were co-genetic. The fluorites display elevated(La/Yb)Nratios, which decrease from 1201 to 5710 for green fluorites to 689–1568 for violet fluorites, indicating that they precipitated at the early hydrothermal sulfide stage,and Pb–Zn ores crystallized earlier than pyrite ores. The similar Tb/La ratios of the fluorites also indicate that they precipitated at an early stage within a short time. From the green fluorites to violet fluorites, the total rare earth element(ΣREE)concentrationsdecreasefrom1052–1680 ppm to 148–350 ppm, indicating that the green fluorites precipitated from a more acidic fluid. The Eu/Eu*ratios increase from 0.17 to 0.30 for green fluorites to0.29–0.48 for violet fluorites, and the Ce/Ce* ratios decrease from 1.08–1.13 to 0.93–1.11, suggesting a gradual increase in oxygen fugacity(fO_(2)) and pH value of the mineralization fluid. Though the fluorites display similar REE patterns to the granodiorite-porphyry and limestone,the ΣREE concentrations of the fluorites are significantly higher than those of limestone and the granodiorite-porphyry, suggesting that an important undetected non-magmatic source is involved to provide sufficient REE for fluorites. The most plausible mechanism is fluid mixing between magma fluid and an undetected non-magmatic fluid.

Fluorite REE characteristics of the Diyanqinamu Mo deposit,Inner Mongolia, China

The Diyanqinamu Mo deposit, a newly discovered porphyry deposit in the northern-central part of the Great Xing'an Range, Inner Mongolia, China, is characterized by widely distributed fluorite. It is important to note that almost all the fluorite that is paragenetic with molybdenite is purple. The Tb/Ca–Tb/La ratios of these purple fluorite samples show that they have a hydrothermal origin.The unidirectional solidification texture at the apex of the aplitic granite and the low F contents in the andesite suggest that most of F in fluorite was derived from granitic melts. These observations suggest that the fluorite was related to the magmatic-hydrothermal fluids. All the fluorite separates have consistent total REE contents with LREE-depleted, HREE-enriched, negative Eu anomaly,unapparent Ce anomaly and positive Y anomaly. These characteristics are significantly different than those of country granite, andesite and tuff whole-rock. The positive Y anomaly of the fluorite separates implies that the hydrothermal fluids migrated a long distance, as suggested by the fact that the fluorite-molybdenite veins were mostly hosted in andesite and tuff, far from the Mo ore-forming granites. The features of LREE-depleted and HREE-enriched fluorite are due to the REE-complex in the F-enriched fluids during migration. The stronger negative Eu anomaly of fluorite than those of country rocks suggests that the Eu anomaly of the original hydrothermal fluid was enhanced by the high temperature(generally above 200 or250 °C). The widespread magnetite in the studied deposit indicates that the magmatic-hydrothermal fluid was oxidized at early stage. On the other hand, the pyrite was also paragenetic, with the molybdenite and unapparent Ce anomaly implying that the hydrothermal fluid probably experienced oxygen fugacity decreasing during migration,which is important for Mo mineralization.

Fundamental Research on Comprehensive Exploitation and Utilization of Paragenetic Fluorite in Bayan Obo deposit of Inner Mongolia,China

Bayan Obo deposit in Inner Mongolia,China is not only the largest Iron-LREE-niobium deposit known in the world but also a giant fluorite deposit.Banded and streaky fluorite-rich REE-iron ores,bastnasiteapatite -pyroxene-fluorite ores,high-Fe,REEs,and fluorite ores,monazite(bastnaesite)-fluorite(low-Fe, high REE) ores etc.are widely disseminated in the Main and the East ore bodies.In 1985,proven

Magnetite-Fluorite Rock:A New Rock Type of Hot Water Sedimentation

The new type hot water sedimentary rock -- magnetite-fluorite rock occurs as quasi-layers in flat parts of contact zones between rock body and strata in Bamianshan of Changshan County, Zhejiang Province, China. The main mineral assemblage is fluorite＋magnetite＋cassiterite. The rock shows typical laminated structure and obvious mosaic texture. Its formation temperature is between 123℃-160℃, averaging at 142℃. The major chemical composition of the rock includes CaF2, SiO2, Al2O3, FeO, and Fe2O3; the high-content microelement association includes W, Sn, Be, Rb, Sr, S, and CI; and the total content of REE is low （∑REE between 35.34×10^-6-38.35×10^-6）, showing LREE enrichment type of distribution pattern. Diagenesis： driven by the tectonic stress, the formation water heated in the deep strata had moved along the fissures or fractures in strata and had extracted components from the strata on the way, and finally stagnated in the flat parts of contact zones between rock body and strata. With drop in temperature, magnetite and fluorite were separated from the hot water and precipitated alternately, forming this hot water sedimentary rock with new type mineralogical composition, typical laminated structure, obvious mosaic texture and sub-horizontal occurrence. The characteristics of the new type mineralogical composition, sedimentary tectonic environment and chemical composition are different from that of the well-known traditional hydrothermai sedimentary rocks.

The Formation Mechanism and Geological Significance of Fluorite in Ordovician, Central Uplift of Tarim Basin

Based on analysisof karst fracture-vuggy filling mineralogy and geochemical fluorite in hercynian, this paper make further research about formation and significance of fluorite in central uplift of Tarim Basin. It is point out that the development of hercynian fracture-vuggy and filling succession of fracture-cave mineral was under the background of the mingling of low-temperature magma hydrotherm and the brine of upper strata. There are overlap or associate relations between generate of fluorite and buried dissolution or oil-gas migration. It was volume decreased 26.4% after calcite metasomatic by fluorite, this reaction made fluorite engender plentiful intergranular space. It’s created appreciable reservoir space. At same time, hydrotherm carried by fluorite generating could erode adjacent rock though fracture or fissure, forming irregular fracture-cave system, and also accompanied with hydrocarbon migration. The time of hydrocarbon migration and accumulation happened in late hercynian-indosinian is inosculates with the sedimentation time such as fluorite and several hydrothermal mineral.

FLOTATION MECHANISM OF FLUORITE AND HEMATITE WITH SODIUM NAPHTHENE SULFONATE

ＦＬＯＴＡＴＩＯＮＭＥＣＨＡＮＩＳＭＯＦＦＬＵＯＲＩＴＥＡＮＤＨＥＭＡＴＩＴＥＷＩＴＨＳＯＤＩＵＭＮＡＰＨＴＨＥＮＥＳＵＬＦＯＮＡＴＥ￥Ｇｅ，Ｙｉｎｇｙｏｎｇ；Ｑｕｅ，Ｘｕａｎｌａｎ（ＣｈａｎｇｓｈａＲｅｓｅａｒｃｈＩｎｓｔｉｔｕｔｅｏｆＭｉｎｉｎｇ...

Efficient CO_2 Electrolysis with Fluorite Structure Nanoparticles Modified Perovskite Structure La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3-δ) Cathode

Perovskite structure La_（0.75）Sr_（0.25）Cr_（0.5）Mn_（0.5）O_（3-δ）（LSCM） cathode with unique structure can electrolyze CO_2 to CO in solid oxide electrolysers（SOEs）.However,the cell performance is restricted by its electro-catalysis activity.In this work,fluorite structure nanoparticles（CeO_（2-δ）） are impregnated on LSCM cathode to improve the electro-catalysis activity.X-ray diffraction（XRD）,scanning electron microscope（SEM） and X-ray photoelectron spectroscopy（XPS） together approve that the fluorite structure nanoparticles are uniformly distributed on the perovskite structure LSCM scaffold.Electrochemical measurements illustrate that direct CO_2 electrolysis with 10%mol CeO_（2-δ） impregnated LSCM cathode exhibits excellent performance for current density（0.5 A×cm^（-2）） and current efficiency（～95%） at 800 ℃ under 1.6 V.It is believed that the enhanced performance of directed CO_2 electrolysis may be due to the synergetic effect of fluorite structure CeO_（2-δ） nanoparticles and perovskite structure LSCM ceramic electrode.