CaO-NaCl体系焙烧混合稀土精矿的研究

采用TG-DTA热分析技术研究CaO-NaCl体系焙烧混合稀土精矿的分解过程。结果表明:添加CaO-NaCl后,混合稀土精矿的分解过程分为两个阶段,第一阶段在405℃～498℃区间主要是氟碳铈矿的分解,第二阶段在670℃～730℃区间主要是CaO和矿物中的CaCO3分解独居石和稀土氟氧化物。并选择了焙烧温度、CaO加入量、NaCl加入量为影响因素,用二次正交回归实验设计方法研究了混合稀土精矿分解率随三因素而变化的规律,得出了相应的回归方程。通过分析讨论,得到了CaO-NaCl体系焙烧混合稀土精矿的合理工艺条件:温度780℃、CaO加入量15%(质量分数)、NaCl加入量10%(质量分数)。

CaO-NaCl焙烧分解独居石的研究

研究了630℃～870℃焙烧温度范围内,CaO、NaCl对独居石分解率影响的变化规律,得出了相应的回归方程,并且用该方程讨论了CaO、NaCl、焙烧温度对独居石分解率的影响。研究结果表明:独居石分解率随CaO、NaCl增加、焙烧温度的升高而增加。当CaO和NaCl加入量分别都为45%,焙烧温度为870℃时,独居石的分解率达到78.39%。

Reaction process of monazite and bastnaesite mixed rare earth minerals calcined by CaO-NaCl-CaCl_2

The decomposition reactions of monazite and bastnaesite mixed rare earth minerals calcined by CaO-NaCl-CaCl2 were studied by means of TG-DTA and XRD. The results show that the process of the minerals decomposed by CaO involves two steps. The first step occurs in the temperature range of 425-540 ℃, and the main reactions are bastnaesite decomposition, i.e. REOF reacts with CaO to produce RE2O3 and CaF2, and Ce2O3 is oxidized to CeO2. During this step, CaCO3 is formed at about 500 ℃. The second step takes place in the temperature range of 610-700 ℃, and the reactions are monazite decomposition into RE2O3, Ca5F(PO4)3 and Ca3(PO4)2 by CaO and CaF2. In this process, the decomposition ability is improved because CaO from CaCO3 decomposing has high chemical activity. In calcining process, the new formed Ca5F(PO4)3 restrains fluorine that can escape in form of gaseous compound. The decomposition ratio of the mixed rare earth minerals reaches 90.8% at 700 ℃.

以NaCl-CaCl_2为助剂CaO分解氟碳铈矿的研究

现行分解氟碳铈矿过程中,氟以气相形式逸出,既浪费氟资源,又污染环境。为了寻求新的清洁冶金方法,文中采用DTA-TG和XRD热分析技术对CaO-NaCl-CaCl2焙烧标题矿物分解过程的化学反应进行了研究。用二次正交回归实验设计方法研究了氟碳铈矿分解率随四因素而变化的规律,得出了相应的回归方程,并得出的优化工艺条件:温度:700℃;CaO加入量:15%(质量百分数);NaCl加入量10%(质量百分数);焙烧时间:60 min,分解率为92.14%。通过分析讨论可知:由于CaO的加入,氟以CaF2固体的形式存在于焙烧产物中,抑制了气相氟的产生,本文采用的方法是一种清洁冶金工艺。

Study on Escaping Fluorine Inhibition in Calcining Process of Mixed Rare Earth Concentrate

GC technology was used to study escaping fluorine in calcined process of mixed rare earth concentrate. The mixed rare earth concentrate and it adding assistant of CaO-NaCl-CaCl2 were calcined at 400～750 ℃ for 30～120 min, and then total amount of fluorine, exhausting ratio of fluorine, decomposition ratio and the component were determined. The results showed that adding CaO-NaCl-CaCl2 the decomposition ratio was up to 90% at 700 ℃ in 1 h, and the escaping ratio of fluorine decreased from 29.52% to 0.948%. The average inhabitation ratio was 98.39%. This method supplied basis for low energy and clean decomposition of mixed rare earth concentrate.

Influence of NaCl-CaCl_2 on Decomposing REPO_4 with CaO

The influence of NaCl-CaCl2 on thermal decomposition of REPO4（RE： Ce, La, Nd, Th） with CaO was studied. The heat decomposing process of REPO4 was tested with TG-DTA experiments. The results showed that the decomposition temperature of REPO4 with CaO was reduced because of adding NaCl-CaCl2 mixture （NaCl：CaCl2 = 1：1 ）. The influence of the addition of NaCl-CaCl2, roasting temperature and roasting time on decomposition ratio of REPO4 with CaO was studied. The results showed that the decomposition ratio of REPO4with CaO was 79% when the addition percentage of NaCl-CaCl2 was 10%, the roasting temperature was 750℃, and the roasting time was 1 h.

抑制混合型稀土精矿焙烧过程中氟逸出的研究

利用气相色谱技术研究含混合稀土精矿焙烧过程中氟逸出的问题,分别对混合稀土精矿和加入一定量CaO-NaCl-CaCl2助剂的混合稀土精矿在400～750℃下焙烧30～120min的各个条件进行实验,测出不同条件下焙烧气体中的氟总量、逸出率、分解率以及焙烧产物的物相组成。结果表明:70%的环境湿度下,焙烧混合稀土精矿过程中氟的逸出率随焙烧温度和时间的增加而增大,其中焙烧温度的影响较大,750℃下焙烧2h时可达29.952%;添加CaO-NaCl-CaCl2助剂不仅降低了混合稀土精矿的分解温度,使混合稀土精矿在700℃下焙烧2h的分解率在90%以上,更重要的是抑制了焙烧过程中氟的逸出,使氟的逸出率由19.296%下降为0.315%,相对抑制作用为98.37%。

Kinetics of mixed rare earths minerals decomposed by CaO with NaCl-CaCl_2 melting salt

For increasing reaction rate and reducing decomposing temperature,TG-DTA,XRD,SEM and Chemical analysis were used to study the kinetics of mixed rar e earths minerals decomposed by CaO with NaCl-CaCl2. The results showed that the reaction rate increased with increasing of NaC-CaCl2 addition,CaO addition,an d decomposition temperature. The kinetics of mixed rare earths minerals decompos ed by CaO conformed to 1-2/3X-(1-X) 2/3=kdt mode. The decomposition reaction rate was controlled by two steps,and the activation energy was decreased with addin g of NaCl-CaCl2 melting salt. The micro-pattern of products was loosening and po rous with NaCl-CaCl2 in decomposition system.