P_（204）-HCl-H_3AOH体系萃取分离轻稀土元素的基础研究
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摘要
稀土元素具有特殊的物理与化学性能,因而在冶金、石油化工、玻璃陶瓷领域和各种功能材料中广泛应用。为了从混合稀土原料中获得单一稀土元素或某几种稀土元素,现工业上主要采用氨水或碳酸氢铵皂化的P204[二(2-乙基己基磷酸)]或P507[2-乙基己基膦酸单乙基己基脂]萃取剂分离稀土元素,但该方法产生含有很高浓度NH4+的废水,对环境污染严重。
     针对现有分离稀土的工艺和研究的不足,本论文通过在稀土氯化物溶液中加入配合剂柠檬酸(H3AOH),采用非皂化的P204萃取剂分离轻稀土元素。研究了该体系中P204萃取轻稀土元素的分配比、分离系数、萃取饱和容量与酸度、柠檬酸浓度和稀土浓度的关系,并对萃取轻稀土的机理及动力学进行了系统的研究。
     文中采用单级萃取实验方法研究了不同稀土料液、酸度和柠檬酸浓度条件下,在P204-HCl-H3AOH体系中轻稀土元素的分配比和萃取饱和容量,并采用回归分析法建立了以料液酸度、柠檬酸浓度和稀土浓度为变量的三元一次回归方程,分析了酸度、柠檬酸浓度和稀土浓度三因素对轻稀土的分配比和分离系数的影响。结果表明：当料液酸度pH值为1.0、柠檬酸浓度为0.25mol·L-1、稀土浓度为0.25mol·L-1时,轻稀土元素的分配比最大达到DLa=0.1767、DCe=0.7353.DPr=1.5221和DNd=2.4201,轻稀土元素间最大分离系数分别为βCe/La=4.16、βPr/Ce=2.07和βNd/Pr=1.59。同样工艺参数下,在串级萃取分离轻稀土的生产线上得到有效级平均分离系数分别是βCe/La=3.50、βPr/Ce=2.05和βNd/Pr =1.35,此值均高于该生产线皂化的P204萃体系中βCe/La=2.14、βPr/Ce=1.67和βNd/Pr=1.33。并且随着柠檬酸浓度的升高,P204萃取稀土的容量逐渐增大,最大可以达到29.71 g·L-1比盐酸体系提高近50%。
     通过实验结果得出P204在含有柠檬酸体系中与轻稀土离子的萃取平衡常数分别为：当pH>1时,1gKLa=-1.77、1gKce=-1.63、1gKPr=-1.26、1gKNd=-0.86；当0     采用红外光谱分析方法从萃取剂分子结构的变化研究了P204-HCl-H3AOH体系萃取稀土离子的机理,结果表明：当pH>1时萃取反应是稀土离子与P204分子的P-OH基团H+置换,其属于阳离子交换机制；当0     采用恒界面法研究了P204-HCl-H3AOH体系萃取轻稀土的动力学,实验发现P204萃取轻稀土的速率随着搅拌速度、温度和比界面积的增大而增大,根据阿仑尼乌斯方程计算出P204-HCl-H3AOH体系中正向萃取轻稀土的表观活化能分别为ELa=19.11KJ-mol-1 ECe=13.13 KJ·mol-1、EPr=10.22 KJ·mol-1和ENd=8.39KJ·mol-1,表明此过程具有典型的扩散速度控制特征。通过研究酸度和萃取剂浓度对萃取速率的影响,确定P204-HCl-H3AOH体系中P204萃取轻稀土的正向反应速率方程式为：
Since the rare earth (RE) products have particular physical and chemical properties, they are widely used in metallurgy, petrochemical industry, various functional materials and glass ceramic field etc. In order to obtain individual rare earth element or mixed several rare earth elements from mixed rare earth feed, P204 or P507 as extractant saponified by ammonia liquor or ammonium acid carbonate are used to separate rare earth elements, but this method produces drain water contained high concentration NH4+, which heavily give environment pollution.
     In this thesis, the coordination agent citric acid (H3AOH) is added to rare earth and the unsaponified P204 is used as extractant in order to improve the process of separating light rare earth. The distribution ratio of rare earth elements in rare earth chloride solution and P204 extractant, separation coefficient, saturated extraction capacity and acidity, citric acid concentration, rare earth concentration were studied. The mechanics and the kinetics of the light rare earth extraction were studied.
     Under the conditions of different rare earth feed, acidity and citric acid concentration, the distribution ratio of the light rare earths and extraction saturated capacity in P204-HCl-H3AOH system were studied by single stage extraction experiments. The ternary linear regression equation of feed acidity, citric acid concentration and rare earth concentration was obtained, and the effect of them on the distribution ratio and separation coefficient were analyzed. The results show that, when feed acidity pH 1.0, citric acid concentration 0.25mol·L-1 and rare earth concentration 0.25mol·L-1, the max distribution ratio(D) comes up to DLa=0.1767, DCe=0.7353, DPr=1.5221 and DNd=2.4201 respectively, the max separation coefficient(β) areβCe/La=4.16,βpr/Ce=2.07 andβNd/Pr=1-59 respectively. By continuous stage extraction, the average separation coefficient of areβCe/La=3.50,βpr/Ce=2.05 andβNd/Pr=1-35 respectively at the same experiments conditions as single stage extraction, which are higher compare to the saponified P204 systemβCe/La=2.14,βPr/Ce=1-67 andβNd/Pr=1-33. Moreover, the capacity of unsaponified P204 extracting rare earth increases with citric acid concentration, its maxium is 29.71 g·L-1, which increases nearly 50% compare to soaponified P204.
     The extraction equilibrium constants(K) of unsaponified P204 in the citric acid system are 1gKLa=-1.77, 1gKCe=-1.63, 1gKPr=-1.26, 1gKNd=-0.86 when pH>1; and 1gKLa=-0.61,1gKCe =0.13,1gKpr=0.40,1gKNd=0.80 when 0     The mechanics of extracting rare earth ion in P204-HCl-H3 AOH system were determined by infrared spectrum analysis. The results show that, extraction reaction are the replacement of H+of P-OH with rare earth ions according to cation exchange mechanics when pH>1. When 0     The kinetics of extracting the light rare earth in P204-HCl-H3AOH system was investigated by constant interfacial area method. The results show that, the rate of P204 extracting light rare earths increases with stirring speed, temperature, specific interfacial area. According to Arrhennius equation, the apparent activation energy of extracting light rare earths are ELa=19.11KJ·mol-1, ECe=13.13 KJ·mol-1, EPr=10.22 KJ·mol-1 and ENd= 8.39 KJ·mol-1 respectively, which illustrates that this process has obvious diffusion velocity control characteristic. By studying the effect of acidity and extractant concentration on extraction rate, the positive reaction rate equations of extracting light rare earths in P204-HCl-H3AOH system are determined as fellows:
引文
综合国内外有关的研究可知,协同萃取和配合交换萃取分离方法均有替代现行的皂化萃取工艺,实现清洁冶金工艺的可能性。两种方法相比,后者可在现有的酸性磷型萃取萃体系工艺中仅添加少量的配合剂,而无需对原生产线进行改动,生产操作简单,易于生产控制和生产环境好的特点,更便于将我国已形成的皂化P507(或P204)体系改造成非皂化体系。这符合又好又快的解决目前稀土萃取分离生产废水污染环境问题的国策方针。但是至今为止的配合交换萃取的研究尚存在两个制约其在大规模生产中应用的问题：
    ①仅限于特定稀土组成的溶液,缺乏从轻稀土矿物组成的溶液中分离稀土元素的萃取工艺及基础研究,这对于迫在眉睫的从稀土分离生产源头解决铵氮废水污染环境的社会需要而言无疑是个缺憾；
    ②配合交换分离稀土元素方法中以DTPA、EDTA效果最好,但回收DTPA、EDTA主要采用蒸发水分-调整酸度-结晶析出方法,其工艺过程复杂、能耗高,回收利用率低,再加上配合剂的售价较高,导致生产成本大幅度升高,因此限制了该方法在大规模生产中的应用。
    针对现有研究的不足,本文通过在稀土氯化物溶液中加入配合剂柠檬酸(H3AOH),采用非皂化的P204萃取剂分离轻稀土元素,研究轻稀土元素的分配比和分离系数与酸度、柠檬酸浓度的关系问题。其目的是为开发一种生产成本低,无氨氮污染的清洁分离工艺提供理论依据。
    本文的主要研究内容如下：
    (1)研究HCl-H3AOH溶液中不同稀土料液酸度、柠檬酸浓度和稀土浓度对轻稀土元素分配比、分离系数和饱和萃取容量的影响,并建立相应的数学关系式。
    (2)通过红外光谱分析负载La、Ce, Pr、Nd的元素的萃取剂分子结构变化,确定HCl-H3AOH溶液中轻稀土离子分别与P204萃取剂的萃合机理。
    (3)得出HCl-H3AOH溶液中轻稀土离子与分别P204萃取剂的有效萃合反应常数。
    (4)研究HCl-H3AOH溶液中轻稀土离子分别与P204萃取剂动力学反应的机理,推导得出反应的反应速率方程式,求出萃取反应的动力学参数以及反应活化能确定控制步骤并得出动力学反应方程。
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    2.5.2多元线性回归方程的方差分析表示Y与X1X2X3…Xm线性关系的密切程度。表2.2三元线性回归方程方差分析表Table 2.2 variance analysis of ternary linear regression equation
    查F分布表F(3,59)α,若F>F(3,59)α,则认为回归方程在α水平上显著,若α=0.01,则称方程为高度显著；若α=0.05则称方程为显著；若F<(3,59)α,则方程不显著。
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    4.在P204-HCl-H3AOH体系中随着柠檬酸浓度的升高,P204萃取稀土的饱和容量逐渐增大,最大可以达到29.71 g·L-1,比不含柠檬酸的P204-HCl的有机相萃取饱和容量20g·L-1提高近50%。
    5.串萃取实验得出稀土元素有效级的平均分离系数分别是βCe/La=3.5、βPr/Ce= 2.05、βNd/Pr=1.35,此值均高于皂化的P204萃体系中βCe/La=2.14、βPr/Ce=1.67、β Nd/Pr=1.33。这些结果说明串级萃取的各级中,柠檬酸有效的发挥了同稀土元素的配合作用,促进了萃取剂负载的稀土元素与水溶液稀土元素的交换作用。因此采用非皂化P204-HCl-H3AOH体系串级萃取分离轻稀土元素是可行的。
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    4.5本章小结
    1.采用红外光谱分析方法对柠檬酸在水溶液中和P204-HCl与P204-HCl-H3AOH体系萃取稀土离子后的有机相的研究表明,柠檬酸在萃取体系中仅存在于水相中,稀土以未配合的形式萃入有机相,即柠檬酸不参加萃取反应。
    2.采用外光谱分析方法确定P204-HCl-H3AOH体系萃取稀土离子的机理,当pH>1时萃取反应是稀土离子与P-OH置换,按照阳离子交换机制进行的；当0    3.通过研究P204从含柠檬酸的稀土氯化物溶液萃取稀土的机理的表明,当0    4.计算得出P204在含有柠檬酸体系中与轻稀土离子的萃取平衡常数分别为：当pH>1时：1gKLa=-1.77、1gKCe=-1.63、1gKP=-1.26、1gKNd=-0.86。当0    La、Ce、Pr、Nd的萃取平衡常数表明,它们的萃取平衡常数随着原子序数的增加而增大,说明在P204-HCl-H3AOH体系中P204萃取轻稀土为“正序萃取”。P204分别萃取各轻稀土元素的萃取平衡常数间的差值比水相中柠檬酸与各轻稀土元素间配合稳定常数的差值大的现象,解释了P204-HCl-H3AOH体系中轻稀土间的分离系数增大的原因。
    5.配合不同稀土元素的P204红外光谱图表明从La→Nd轻稀土离子与P204的结合能力增强,并且P204-HCl-H3AOH体系中P204萃取相同稀土离子时P=O基团的变化比P204-HCl体系的大,这进一步解释了柠檬酸作用稀增大分离系数的原因。
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    4.通过对萃取机理推导所得轻稀土萃取的速率方程与实验所得轻稀土萃取的速率方程式比较,从而验证萃取速率方程和萃取机理的推测是正确的。
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