浓NaOH溶液分解包头混合稀土矿的工艺研究
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摘要
随着科技的迅速发展,绿色、环保理念的深入人心,碱法分解包头稀土精矿工艺越来越受到人们的青睐。为克服现有碱法生产工艺中首先要进行化学选矿而使生产不连续的缺点,本文对浓碱法直接分解包头混合稀土矿工艺进行了研究,实验采用包头混合稀土矿与70%的氢氧化钠溶液混合焙烧,反应由开始时的固-液相反应到结束时的固-固相反应,研究了反应前后相变化的工艺条件对稀土分解率的影响。
论文主要内容有以下三个方面：
1.机理探讨。
对包头稀土精矿添加NaOH进行了热分析研究,探讨该复杂体系的热分解机理。
2.静态条件下稀土矿物的焙烧分解及浸出。
研究了包头稀土矿中钙在工艺过程中对稀土分解率及回收率的影响。通过对比实验数据表明,在本工艺研究中,除钙和不除钙时稀土浸出率相差较小,说明钙的存在不是影响稀土分解率的主要因素,因此,不进行化学选矿除钙而直接进行稀土精矿的碱分解工艺是可行的。
采用一个三因素四水平的正交实验,探讨在静态条件下矿碱比、焙烧温度和焙烧时间对稀土分解率的影响。结果表明矿碱比对焙烧反应影响最大,其次为焙烧温度和焙烧时间,试验得到了最佳工艺条件：矿碱比为1：1,焙烧温度为400℃,焙烧时间为90min。稀土分解率可以达到84.80%。
静态焙烧实验中,随着焙烧温度的升高,F在焙烧矿中含量降低,400℃以后反应的固氟效果变差,氟以气体形式逸出污染空气。
3.动态条件下稀土矿物的焙烧分解及浸出。
采用矿碱比为1：1,分别在低温和中温条件下,对不同品位的稀土精矿与70%的NaOH溶液混匀后进行动态焙烧。实验结果显示,动态焙烧下,50%以上品位稀土精矿的稀土分解率可达到93.84%,最高达98.44%。
在动态焙烧实验中,氟碳铈矿分解较完全,水洗后F以F形式存在于水洗液中。焙烧矿经酸溶后,98%以上的Th以Th4+存在于稀土浸出液中,即经碱分解后的渣为非放射性渣,且渣量小。
该碱分解工艺可以去除传统工艺的“酸洗除钙”工序,工艺连续,工艺过程无废气和放射性废渣,稀土、钍、氟和磷等均得到回收,达到了清洁生产和资源综合利用的目的。
With the rapid development of science and technology, and the sense of environmental protection is deep into people's mind, the technology of alkali decomposing of Baotou rare earth concentrate is becoming favored gradually. In this thesis, the technics for direct decomposition of Baotou rare earth concentrate by concentrated alkali has been studied. The experiment was carried out by roasting of the mixture of Baotou rare earth concentrate and 70% NaOH solution. It was solid-liquid reaction in the start, and changed into solid-solid reaction in the end. The influence of the phase change before and after the reaction on the decomposition efficiency of the rare earth was also investigated.
The main contents of the thesis could be divided into three parts:
1. Mechanism discussion
Thermogravimetry and differential thermal analysis of Baotou rare earth concentrate with the addition of NaOH were carried out, and the thermal decomposition mechanism of the complex system was investigated.
2. The roasting decomposition and leaching of rare earth concentrate at static conditions
The influence of the calcium in Baotou rare earth concentrate on the decomposition efficiency and the recovery ratio of rare earth was investigated in the thesis. The comparison of the experimental results showed that the decomposition efficiencies of rare earth were approximate before and after the removal of calcium, which indicates that the existence of calcium was not the main factor that affecting the decomposition efficiency of rare earth. Therefore, it is possible to carry out the alkali decomposing technology of rare earth concentrate directly without removing calcium by chemical beneficiation.
The orthogonal experiments with three factors and four levels were conducted to investigate the influence of the ratio of rare earth concentrate to alkali, the calcination temperature and time on the decomposition efficiency of rare earth. The results showed that the ratio of rare earth concentrate to alkali is the most influential factor in the reaction, and secondly for calcination temperature and time. The optimum process conditions were obtained by experiments:the ratio of rare earth concentrate to alkali was 1:1, the calcination temperature was 400℃, and the calcination time was 90 minutes. The decomposition efficiency could reach 84.80%.
In the static roasting experiment, the content of fluorine in the calcined rare earth concentrate reduced with the increase of the calcinations temperature. The effect of fluorine fixation became worse over 400℃, and the air contamination will be caused by fluorine in the form of gas.
3. The roasting decomposition and leaching of rare earth concentrate at dynamic conditions
Different grade of rare earth concentrate and 70% NaOH solution were mixed at low and medium temperature, and the ratio of rare earth concentrate to alkali were kept at 1:1, after which the dynamic roasting was conducted. The results showed that the decomposition efficiency of 50% rare earth concentrate could reach 93.84%, and the maximum was 98.44%.
In the dynamic experiments, bastnasite could be decomposed effectively, and the fluorine existed in the form of F- in water after washing. After acid dissolution of the calcined rare earth concentration, over 98% of the thorium existed in the form of Th4+ in the leaching liquid, which means that the residue after alkali decomposing was not radioactive, and the amount of the residue is small.
The alkali decomposing technology could get rid of the pickling procedure in the traditional process. The process is continuous, and there was no production of waste gas and radioactive residue. The chemical elements such as rare earth, thorium, fluorine, and phosphorus could be recycled, which realizes the goal of clean production and resource comprehensive utilization.
论文主要内容有以下三个方面：
1.机理探讨。
对包头稀土精矿添加NaOH进行了热分析研究,探讨该复杂体系的热分解机理。
2.静态条件下稀土矿物的焙烧分解及浸出。
研究了包头稀土矿中钙在工艺过程中对稀土分解率及回收率的影响。通过对比实验数据表明,在本工艺研究中,除钙和不除钙时稀土浸出率相差较小,说明钙的存在不是影响稀土分解率的主要因素,因此,不进行化学选矿除钙而直接进行稀土精矿的碱分解工艺是可行的。
采用一个三因素四水平的正交实验,探讨在静态条件下矿碱比、焙烧温度和焙烧时间对稀土分解率的影响。结果表明矿碱比对焙烧反应影响最大,其次为焙烧温度和焙烧时间,试验得到了最佳工艺条件：矿碱比为1：1,焙烧温度为400℃,焙烧时间为90min。稀土分解率可以达到84.80%。
静态焙烧实验中,随着焙烧温度的升高,F在焙烧矿中含量降低,400℃以后反应的固氟效果变差,氟以气体形式逸出污染空气。
3.动态条件下稀土矿物的焙烧分解及浸出。
采用矿碱比为1：1,分别在低温和中温条件下,对不同品位的稀土精矿与70%的NaOH溶液混匀后进行动态焙烧。实验结果显示,动态焙烧下,50%以上品位稀土精矿的稀土分解率可达到93.84%,最高达98.44%。
在动态焙烧实验中,氟碳铈矿分解较完全,水洗后F以F形式存在于水洗液中。焙烧矿经酸溶后,98%以上的Th以Th4+存在于稀土浸出液中,即经碱分解后的渣为非放射性渣,且渣量小。
该碱分解工艺可以去除传统工艺的“酸洗除钙”工序,工艺连续,工艺过程无废气和放射性废渣,稀土、钍、氟和磷等均得到回收,达到了清洁生产和资源综合利用的目的。
With the rapid development of science and technology, and the sense of environmental protection is deep into people's mind, the technology of alkali decomposing of Baotou rare earth concentrate is becoming favored gradually. In this thesis, the technics for direct decomposition of Baotou rare earth concentrate by concentrated alkali has been studied. The experiment was carried out by roasting of the mixture of Baotou rare earth concentrate and 70% NaOH solution. It was solid-liquid reaction in the start, and changed into solid-solid reaction in the end. The influence of the phase change before and after the reaction on the decomposition efficiency of the rare earth was also investigated.
The main contents of the thesis could be divided into three parts:
1. Mechanism discussion
Thermogravimetry and differential thermal analysis of Baotou rare earth concentrate with the addition of NaOH were carried out, and the thermal decomposition mechanism of the complex system was investigated.
2. The roasting decomposition and leaching of rare earth concentrate at static conditions
The influence of the calcium in Baotou rare earth concentrate on the decomposition efficiency and the recovery ratio of rare earth was investigated in the thesis. The comparison of the experimental results showed that the decomposition efficiencies of rare earth were approximate before and after the removal of calcium, which indicates that the existence of calcium was not the main factor that affecting the decomposition efficiency of rare earth. Therefore, it is possible to carry out the alkali decomposing technology of rare earth concentrate directly without removing calcium by chemical beneficiation.
The orthogonal experiments with three factors and four levels were conducted to investigate the influence of the ratio of rare earth concentrate to alkali, the calcination temperature and time on the decomposition efficiency of rare earth. The results showed that the ratio of rare earth concentrate to alkali is the most influential factor in the reaction, and secondly for calcination temperature and time. The optimum process conditions were obtained by experiments:the ratio of rare earth concentrate to alkali was 1:1, the calcination temperature was 400℃, and the calcination time was 90 minutes. The decomposition efficiency could reach 84.80%.
In the static roasting experiment, the content of fluorine in the calcined rare earth concentrate reduced with the increase of the calcinations temperature. The effect of fluorine fixation became worse over 400℃, and the air contamination will be caused by fluorine in the form of gas.
3. The roasting decomposition and leaching of rare earth concentrate at dynamic conditions
Different grade of rare earth concentrate and 70% NaOH solution were mixed at low and medium temperature, and the ratio of rare earth concentrate to alkali were kept at 1:1, after which the dynamic roasting was conducted. The results showed that the decomposition efficiency of 50% rare earth concentrate could reach 93.84%, and the maximum was 98.44%.
In the dynamic experiments, bastnasite could be decomposed effectively, and the fluorine existed in the form of F- in water after washing. After acid dissolution of the calcined rare earth concentration, over 98% of the thorium existed in the form of Th4+ in the leaching liquid, which means that the residue after alkali decomposing was not radioactive, and the amount of the residue is small.
The alkali decomposing technology could get rid of the pickling procedure in the traditional process. The process is continuous, and there was no production of waste gas and radioactive residue. The chemical elements such as rare earth, thorium, fluorine, and phosphorus could be recycled, which realizes the goal of clean production and resource comprehensive utilization.
引文
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