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

International Journal of Minerals,Metallurgy and Materials 2024年第6期31卷 1198-1207页

作者： Qianqian Lu Haisheng Han Wenjuan Sun Xingfei Zhang Weiwei Wang Bilan Zhang Wensheng Chen Qin Zou School of Minerals Processing and Bioengineering Central South UniversityChangsha 410083China Hunan Nonferrous Chenzhou Fluoride Chemical Co. Ltd.Chenzhou 423000China State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization Baotou Research Institute of Rare EarthsBaotou 014030China Hunan Shizhuyuan Nonferrous Metal Co. Ltd.Chenzhou 423000China

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.

关键词： fluorite calcite nanoscale calcium carbonate waste recovery

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

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Journal of Materials Science & Technology 2023年第19期150卷 217-224页

作者： Liangbin Hu Bin Lu Bowen Xue Shixun Dai School of Materials Science and Chemical Engineering Ningbo UniversityNingbo 315211China Key Laboratory of Photoelectric Detection Materials and Devices of Zhejiang Province Ningbo 315211China

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.

关键词： Transparent ceramics Ho_(2)Zr_(2)O_(7) Magneto-optical ceramics fluorite Optical properties

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Mechanism of phthalic acid collector in flotation separation of fluorite and rare earth

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Journal of Rare Earths 2022年第1期40卷 118-126页

作者： Sheng Chang Mei Li Kai Gao Dongliang Zhang Haijun Duan Linlin Ma Zheng Ruan College of Mining Inner Mongolia University of Science&TechnologyBaotou 014010China Key Laboratory of Green Extraction&Efficient Utilization of Light Rare-Earth Resources Ministry of Education Baotou 014010China Inner Mongolia Key Laboratory of Rare Earth Hydrometallurgy and Light Rare Earth Application Baotou 014010China Inner Mongolia Mining Exploitation Co. Ltd.Hohhot 010020China

The mechanism of phthalic acid,a dicarboxylic acid collector,in flotation separation of fluorite and rare earth(RE)was studied in this paper.The experimental data of flotation show that phthalic acid,as the collector,can realize highly efficient separation of fluorite and rare earth under weakly acidic conditions.The adsorption mechanism of phthalic acid on the surface of fluorite and bastnaesite was analyzed in this paper by means of the zeta potential measurement,the Fourier transform infrared(FT-IR),the X-ray photoelectron spectroscopy(XPS)and the stability constant measurement of active metal ion and phthalic acid coo rdination complex.According to the zeta potential testing results,the surfaces of fluorite adsorb the collector phthalate ion with negative charge under weakly acidic conditions which,in turn,increases its electronegativity and results in the motion of its potential.After the reaction between phthalic acid and fluorite ores under weakly acidic conditions,the peak of the fluorite ores is found to have significant changes in the FT-IR results,indicating strong chemical adsorption on the surfaces of phthalic acid and fluorite ores.According to the XPS analysis,the peak of benzene ring of phthalic acid is as high as 2%on the surface of fluorite,while no obvious characteristic peak of benzene ring is found on the surface of bastnaesite.According to the pH potentiometric titration results,the stability constant Ktotal of calcium phthalate complex within the acid range is higher than the stability constant K’total of cerium phthalate complex,indicating that the complex generated between phthalic acid and Ca^(2+)is more stable than the complex generated between phthalic acid and Ce^(3+).The possible reason is that Ca^(2+),with the highest reticular density,plays a prevailing role in the octahedron structure of fluorite amidst the acidic media.As the active point of flotation,Ca^(2+)works with the carboxyl groups of the collector phthalic acid(-C=O-)to form polycyclic calcium phthalate complex.

关键词： fluorite Bastnaesite Carboxylic acid collector Flotation Equilibrium constants of complexes Rare earths

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FLOTATION MECHANISM OF fluorite AND HEMATITE WITH SODIUM NAPHTHENE SULFONATE

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中国有色金属学会会刊：英文版 1995年第2期5卷 49-54页

作者： Ge, Yingyong Que, Xuanlan(Changsha Research Institute of Mining and Metallurgy, Changsha 410012) Changsha Research Inst of Mining and Metallurgy Changsha China

ＦＬＯＴＡＴＩＯＮＭＥＣＨＡＮＩＳＭＯＦＦＬＵＯＲＩＴＥＡＮＤＨＥＭＡＴＩＴＥＷＩＴＨＳＯＤＩＵＭＮＡＰＨＴＨＥＮＥＳＵＬＦＯＮＡＴＥ￥Ｇｅ，Ｙｉｎｇｙｏｎｇ；Ｑｕｅ，Ｘｕａｎｌａｎ（ＣｈａｎｇｓｈａＲｅｓｅａｒｃｈ... 详细信息

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

关键词： flotation mechanism sodium naphthene sulfonate fluorite hematite

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

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International Journal of Minerals,Metallurgy and Materials 2017年第11期24卷 1201-1210页

作者： Tian-yang Hu Ti-chang Sun Jue Kou Chao Geng Yong-qiang Zhao School of Civil and Resources Engineering University of Science and Technology Beijing Beijing 100083 China Key Laboratory of Ministry of Education of China for Efficient Mining and Safety of Metal Mines Beijing 100083 China

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.

关键词： seaside titanomagnetite blast furnace dust co-reduction roasting fluorite mechanisms

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Thermodynamic Analysis of Formation of Fluoride from Gangue in Bayan Obo Iron Concentrate Containing fluorite

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Journal of Iron and Steel Research(International) 2015年第3期22卷 213-218页

作者： Fang ZHANG Sheng-li AN Yi-ci WANG Guo-ping LUO Xiao-long SONG School of Metallurgical and Ecological Engineering University of Science and Technology Beijing School of Materials and Metallurgy Inner Mongolia University of Science and Technology

In order to fill up the deficiency of the theoretical basis about fluoride formation during Bayan Obo iron concentrate roasting process, the thermodynamic conditions of the interactivity between the components of the gangue and calcium fluorite were studied by means of thermodynamic calculation, DTA-TG thermal analysis and XRD characterization. The results revealed that KF, NaF and SiF4 （gaseous） could he,formed during the roasting process, and the tendency of the generation of KF is greater than that of NaF or SiF4 in standard state. Besides, the results of roasting experiments showed that the products of KCaCO3 F and KCaF3 formed in the temperature range of 800-1250 ℃and KF appears when the roasting temperature was higher than 1250 ℃ in K2O-CaF2 system. For the Na2O-CaF2 system, the product of NaF appears at temperature higher than 1050 ℃. The formation reaction of gaseous SiF4 with solid phase CaO · SiO2 in SiO2-CaF2 system took place＂only＇at temperature higher than 1 150 ℃. In the natural potash feldspar-CaF2-CaO system, the fluorination reaction products involved KF at temperature higher than 1 270 ℃ , while in the natural aegirine-CaF2-CaO system, NaF formed at terhperature higher than 980 ℃ during roasting process.

关键词： fluoride Bayan Obo iron concentrate thermodynamic analysis gangue fluorite

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

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China Geology 2020年第3期3卷 473-489页

作者： Bei-bei Han Peng-qiang Shang Yong-zhang Gao Sen Jiao Chao-mei Yao Hao Zou Min Li Liang Wang Hou-yi Zheng China Chemical Geology and Mine Bureau Beijing 100013China b Sinosteel Mining Co. Ltd.Beijing 100080China College of Earth Sciences Chengdu University of TechnologyChengdu 610059China Key Laboratory of Tectonic Controls on Mineralization and Hydrocarbon Accumulation of Ministry of Natural Resources Chengdu 610059China School of Earth Sciences and Resources China University of GeosciencesBeijing 100083China

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.

关键词： fluorite Deposit type Metallogenic regularity Metallogenic belt Prospective prediction Mineral exploration engineering China

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

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Acta Geologica Sinica(English Edition) 2001年第2期75卷 204-211页

作者： WANG Lijuan WANG Jingbin WANG Yuwang MAO Qian Institute of Geology and Geophysics Chinese Academy of SciencesA-11 Datun RoadBeijing 100101 Beijing Institute of Geology for Mineral Resources Beijing 100012

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.

关键词： skarn deposit fluorite fluid-melt inclusion daughter mineral melt composition

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

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Acta Geologica Sinica(English Edition) 2007年第4期81卷 622-636页

作者： HUANG Zhilong XU Cheng Andrew McCAIG LIU Congqiang WU Jing XU Deru LI Wenbo GUAN Tao XIAO Huayun The Key Laboratory of Ore Deposit Geochemistry Institute of Geochemistry Chinese Academy of Sciences Guiyang Guizhou 550002 China The School of Earth Sciences University of Leeds Leeds LS2 9JT UK Department of Geology Kunming University of Technology and Science Kunming Yunnan 650093 China Guangzhou Institute of Geochemistry Chinese Academy of Sciences Guangzhou Guangdong 550002 China

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.

关键词： fluorite REE geochemistry ore-forming fluid Maoniuping REE deposit

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TXD as selective depressand of fluorite and calcite

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中国有色金属学会会刊：英文版 1994年第3期4卷 49-52页

作者： Tian, Xueda Zhu, Jianguang(Department of Mineral Processing Engineering,Central South University of Technology,Changsha 410083)

ＴＸＤＡＳＳＥＬＥＣＴＩＶＥＤＥＰＲＥＳＳＡＮＴＯＦＦＬＵＯＲＩＴＥＡＮＤＣＡＬＣＩＴＥＴｉａｎ，Ｘｕｅｄａ；Ｚｈｕ，Ｊｉａｎｇｕａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＭｉｎｅｒａｌＰｒｏｃｅｓｓｉｎｇＥｎｇｉｎｅｅｒｉｎ... 详细信息

ＴＸＤＡＳＳＥＬＥＣＴＩＶＥＤＥＰＲＥＳＳＡＮＴＯＦＦＬＵＯＲＩＴＥＡＮＤＣＡＬＣＩＴＥＴｉａｎ，Ｘｕｅｄａ；Ｚｈｕ，Ｊｉａｎｇｕａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＭｉｎｅｒａｌＰｒｏｃｅｓｓｉｎｇＥｎｇｉｎｅｅｒｉｎｇ，ＣｅｎｔｒａｌＳｏｕｔｈＵｎｉ...

关键词： flotution depressant fluorite calcite

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