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.

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.

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.

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.

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.

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.

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.

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.

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.

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

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

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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.

TXD as selective depressand of fluorite and calcite

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Minerogenetic Model for Two Types of Fluorite Deposits in Southeastern China

On the basis of the studies of field geology, strontium, hydrogen and oxygen isotopes and REEgeochemistry, coupled with the dating of mineralization, the authors suggest a minerogenetic model of circula-tion and drawing of Late Cretaceous geothermal waters for the fluorite deposits in southeastern China. Thismodel includes two types of mechanism: 1) the leaching-out and drawing through deep circulation of thegeothermal water, and 2) the leaching-out and drawing through shallow circulation of the water. The fluoritemineralization of Mesozoic volcanic rock terrain is related mainly to the former mechanism, with the mineraliz-ing material coming chiefly from the Precambrian metamorphic rocks of the basement underlying the hostrocks; while that of Yanshanian granite terrain is associated with the latter mechanism, with the mineralizingmaterial derived primarily from the host granites and sedimentary rocks.

High-temperature elemental segregation induced structure degradation in high-entropy fluorite oxide

Fluorite-structured oxides constitute an important category of oxides with a wide range of high-temperature applications.Following the concept of high entropy,high-entropy fluorite oxides(HEFOs)have showcased intriguing high-temperature application potential.However,unlocking this potential necessitates an assessment of their long-term stability under high-temperature conditions.In this study,we conducted a prolonged heat treatment at 1000℃on typical HEFO,specifically(CeHfZrGdLa)O_(x).After 100 h,high-intensity X-ray diffraction(XRD)revealed a transition from a single-phase fluorite to a multi-phase configuration.Further investigation by analytical electron microscoy(AEM)demonstrated that this degradation resulted from facilitated element diffusion and consequent escalating chemical fluctuation at high temperatures,leading to spontaneous segregation and separation of Ce and La elements,forming Ce-rich,La-poor,and La-rich phases.Notably,the La-rich phase spontaneously transformed from a fluorite structure(space group Fm3m)to a bixbyite structure(space group Ia3)at elevated temperatures,resulting in the appearance of superstructure reflection in XRD profiles and electron diffraction patterns.Despite the intricate phase decomposition,the energy band gap showed minimal variation,suggesting potential property stability of(CeHfZrGdLa)O_(x)across a broad range of compositions.These findings offer valuable insights into the future applications of HEFOs.

Production and characterization of highly transparent novel magneto-optical Ho_(2)Zr_(2)O_(7) ceramics with anion-deficient fluorite structures

Based on material design idea,we employ a co-precipitation strategy to obtain sinterable Ho_(2)Zr_(2)O_(7) flu-orite particles,successfully leading to novel transparent Ho_(2)Zr_(2)O_(7) ceramics with good optical/magneto-optical properties.The resulting precipitation precursor is identified to be hydrated basic carbonate upon calcination at the optimum temperature of 1250℃into near-spherical Ho_(2)Zr_(2)O_(7) nanopowder with an average size of~64 nm and unimodal narrow size distribution.The crystal intrinsic oxygen defect in fluorite ceramic generally exists in the form of F+center.The best bulk specimen achieved in this work exhibits a high refractive index of~2.1 and a high transparency of~74.4%at 1000 nm comparable with the corresponding defect-free single crystal(~76.4%in theory).In the Ho_(2)Zr_(2)O_(7) structure system,the elec-tronic polarizability of O_(2)-anion generally remains constant around 2.2?3 in the visible region and the corresponding optical basicity is approximately 0.9.The developed magneto-optical transparent Ho_(2)Zr_(2)O_(7) ceramic has Verdet constants of-180±3,-157±5,-87±2,-54±2,and-43±2 rad T^(-1) m^(-1) at 515,635,780,980,and 1064 nm,respectively,which are roughly 1.2-fold higher than the commercial TGG crystal.

Round Top Mountain rhyolite(Texas, USA), a massive, unique Y-bearing-fluorite-hosted heavy rare earth element(HREE) deposit

Round Top Mountain in Hudspeth County, west Texas, USA is a surface-exposed rhyolite intrusion enriched in Y and heavy rare earth elements （HREEs）, as well as Nb, Ta, Be, Li, F, Sn, Rb, Th, and U. The massive tonnage, estimated at well over 1 billion tons, of the deposit makes it a target for recovery of valuable yttrium and HREEs （YHREEs）, and possibly other scarce ele-ments. Because of the extremely fine grain size of the mineralized rhyolite matrix, it has not been clear which minerals host the YHREEs and in what proportions. REE-bearing minerals reported in the deposit included bastn？site-Ce, Y-bearing fluorite, xeno-time-Y, zircon, aeschynite-Ce, a Ca-Th-Pb fluoride, and possibly ancylite-La and cerianite-Ce. Extended X-ray absorption fine struc-ture （EXAFS） indicated that virtually all of the yttrium, a proxy for the HREEs, resided in a coordination in the fluorite-type crystal structure, rather than those in the structures of bastn？site-Ce and xenotime-Y. The YREE grade of the Round Top deposit was just over 0.05%, with 72%of this consisting of YHREEs. This grade was in the range of the South China ionic clay deposits that supply essentially all of the world’s YHREEs. Because the host Y-bearing fluorite is soluble in dilute sulfuric acid at room temperature, a heap leaching of the deposit appeared feasible, aided by the fact that 90%-95%of the rock consists of unreactive and insoluble feld-spars and quartz. The absence of overburden, remarkable consistency of mineralization grade throughout the massive rhyolite, prox-imity （a few km） to a US interstate highway, major rail systems and gas and electricity, temperate climate, and stable political location in the world’s largest economy all enhanced the potential economic appeal of Round Top.

Integrated Exploration Model for Concealed Ore Deposit:A Case Study from Shuitou Fluorite Deposit,Inner Mongolia,North China

The demand for fluorite resource is increasing rapidly as most fluorite deposits on Earth’s surface have been exhausted.The newly discovered fluorite deposits in Inner Mongolia are hosted by Permian metamorphosed sandy slate,intermediate-acid intrusive rocks and Cretaceous volcanic sedimentary rocks.The ore bodies are strictly controlled by faults and buried by cover rocks.The feasibility and effectiveness of multi-techniques for prospecting concealed fluorite ore bodies are evaluated,and 10 anomalies are delineated.On the basis of geological features and effectiveness of different methods,the optimum combinations of ore prospecting techniques are proposed for the exploration of zonal type and burial type concealed fluorite ore bodies.Based on comprehensive researches,an integrated exploration model is proposed:(i)select key prospecting targets based on geological backgrounds,regional geochemical anomalies of F and Ca,and remote sensing images;(ii)identify the spatial distribution of low resistivity anomaly and ore-controlling structure from geophysical survey;(iii)evaluate the mineralization potential in fault zone based on F and Ca anomalies in key sections selected from low resistivity anomaly zones;and(iv)evaluate the mineralization potential and reveal the spatial distribution of fluorite ore bodies and ore-controlling faults based on integrated geophysical and geochemical anomalies.The integrated exploration model is verified to be a powerful tool for prospecting concealed fluorite ore bodies in coverage area.