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.

Geology and mineralization of the Bayan Obo supergiant carbonatite-type REE-Nb-Fe deposit in Inner Mongolia, China: A review

The Bayan Obo supergiant carbonatite-related rare-earth-element-niobium-iron(REE-Nb-Fe) endogenetic deposit(thereafter as the Bayan Obo deposit), located at 150 km north of Baotou City in the Inner Mongolia Autonomous Region, is the largest rare-earth element(REE) resource in the world. Tectonically,this deposit is situated on the northern margin of the North China Craton and adjacent to the Xing’anMongolian orogenic belt to the south. The main strata within the mining area include the Neoarchean Se’ertengshan Group and the Mesoproterozoic Bayan Obo Group. Generally, the rare earth, niobium, and iron mineralization within the deposit are intrinsically related to the dolomite carbonatites and the extensive alteration of the country rocks caused by the carbonatite magma intrusion. The alteration of country rocks can be categorized into three types: contact metasomatism(anti-skarn and skarn alteration), fenitization,and hornfelsic alternation. As indicated by previous studies and summarized in this review, the multielement mineralization at Bayan Obo is closely associated with the metasomatic replacement of siliceous country rocks by carbonatite magmatic-hydrothermal fluids. The metasomatic process is comparable to the conventional skarnification that formed due to the intrusion of intermediate-acid magmatic rocks into limestone strata. However, the migration pattern of Si O2, Ca O, and Mg O in this novel metasomatic process is opposite to the skarn alteration. Accordingly, this review delineates, for the first time, an antiskarn metallogenic model for the Bayan Obo deposit, revealing the enigmatic relationship between the carbonatite magmatic-hydrothermal processes and the related iron and rare earth mineralization.Moreover, this study also contributes to a better understanding of the REE-Nd-Fe metallogenetic processes and the related fluorite mineralization at the Bayan Obo deposit.

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.

Oxygen permeability and CO_2-tolerance of Ce_(0.8)Gd_(0.2)O_(2-δ)-Ln BaCo_2O_(5+δ) dual-phase membranes

A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% LnBaCo2O5＋δ （CGO-LBCO, Ln = La, Pr, Nd, Sin, Gd and Y） were synthesized through a sol-gel route and effects of the Ln3＋ cations on their phase structure, oxygen permeability and chemical stability against CO2 were investigated systemically by XRD, SEM, TG-DSC and oxygen permeation experiments. XRD patterns reveal that the larger Ln3＋ cations （La3＋, Pr3＋ and Nd3＋） successfully stabilized the double-layered perovskite structure of sintered LBCO, while the smaller ones （Sm3＋, Gd3＋, and Y3＋） resulted in the partial decomposition of LBCO with some impurities formed. CGO-PBCO yields the highest oxygen permeation flux, reaching 2.8× 10^-7 mol.s-1.cm-2 at 925 ℃ with 1 mm thickness under air/He gradient. The TG-DSC profiles in 20 mol% CO2/N2 and oxygen permeability experiments with CO2 as sweep gas show that CGO-YBCO demonstrates the best chemical stability against CO2, possibly due to its minimum basicity. The stable oxygen permeation flux of CGO-YBCO under CO2 atmosphere reveals its potential application in the oxy-fuel combustion route for CO2 capture.

Mineralogy and geochemistry of Nb-,Ta-,Sn-,U-,Th-,and Zr-bearing granitic rocks from Abu Rusheid shear zones,South Eastern Desert,Egypt

Granite-hosted,Nb-,Ta-,Sn-,U-,Th-,and Zr(Hf)-bearing mineralization from the Abu Rusheid shear zones occurs about 97 km southwest of the town of Marsa Alam,South Eastern Desert,Egypt.The SSE-trending brittle-ductile Abu Rusheid shear zones crosscut the peralkalic granitic gneisses and cataclastic to mylonitic rocks(mylonite,protomlyonite,and ultramylonite).The northern shear zone varies in width from 1 to 3 m with a strike length of >500 m,and the southern shear zone is 0.5 to 8 m wide and >1 km long.These shear zones locally host less altered lamprophyre and locally sheared granitic aplite-pegmatite dykes.The rare-metal minerals,identified from the peralkalic granitic gneisses and cataclastic to mylonitic rocks are associated with muscovite,chlorite,quartz,fluorite,pyrite,magnetite,and rare biotite that are restricted to the Abu Rusheid shear zones;these are columbite-tantalite and pyrochlore(var.betafite) in the northern shear zone and ferrocolumbite in the southern shear zone.Cassiterite occurs as inclusions in the columbite-tantalite minerals.U-and Th-minerals(uraninite,thorite,uranothorite,ishikawaite,and cheralite) and Hf-rich zircon coexist.Magmatic(?) zircon contains numerous inclusions of rutile,fluorite,U-Th and REE minerals,such as uranothorite,cheralite,monazite,and xenotime.Compositional variations in Ta/(Ta+Nb) and Mn/(Mn+Fe) in columbite range from 0.07-0.42 and 0.04-0.33,respectively,and Hf contents in zircon from 1.92-6.46 of the two mineralized shear zones reflect the extreme degree of magmatic fractionation.Four samples of peralkalic granitic gneisses and cataclastic to mylonitic rocks from the southern shear zone have very low TiO2(0.02 wt%-0.04 wt%),Sr [(15-20)×10-6],and Ba [(47-78)×10-6],with high Fe2O3T(0.94 wt%-1.99 wt%),CaO(0.14 wt%-1.16 wt%),alkalis(9.2 wt%-10.1 wt%),Rb [(369-805)×10-6],Zr [(1033-2261)×10-6],Nb [(371-913)×10-6],U [(51-108)×10-6],Th [(36-110)×10-6],Ta [(38-108)×10-6],Pb [(39-364)×10-6],Zn [(21-424)×10-6],Y [(8-304)×10-6],Hf [(29-157)×10-6],and ∑REE [(64-304)×10-6],especially HREE [(46-167)×10-6].Three samples from the northern shear zone also have very low TiO2(0.03 wt%),Sr [(11-16)×10-6],and Ba [(38-47)×10-6],with high Fe2O3T(1.97 wt%-2.91 wt%),CaO(0.49 wt%-1.01 wt%),alkalis(7.2 wt%-8.3 wt%),Rb [(932-978)×10-6],Zr [(1707-1953)×10-6],Nb [(853-981)×10-6],Ta [(100-112)×10-6],U [(120-752)×10-6],Th [(121-164)×10-6],Pb [(260-2198)×10-6],Zn [(483-1140)×10-6],Y [(8-304)×10-6],Hf [(67-106)×10-6],and ∑REE [(110-231)×10-6],especially HREE [(91-177)×10-6].The very high Rb/Sr(57.5-88.9),and low Zr/Hf(16.9-25.6),Nb/Ta(7.7-9.8),and Th/U(0.21-1.01) are consistent with very frac-tionated fluorine-bearing granitic rocks that were altered and sheared.The field evidence,textural relations,and compositions of the ore minerals suggest that the main mineralizing event was magmatic(629+/-5 Ma,CHIME monazite),with later hydrothermal alteration and local remobilization of the high-field-strength elements.