铜渣中有价组分的选择性析出研究
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摘要
铜渣中含有大量可利用资源，其中包括相当数量的铜及与铜共生贵金属和稀有金属，铜渣中铁的品位一般超过40wt％，远大于冶炼铁矿29.1wt％的平均品位。渣中铁主要分布在橄榄石相和磁性氧化铁相中，而铜主要以细小颗粒弥散于渣中。由于原渣中矿物互相嵌布且晶粒细小，采用传统分离技术回收渣中的铜、铁等组分较为困难。
本文基于铜渣的特点，通过对熔融铜渣的氧化处理，实现渣中铁组分向磁铁矿相选择性富集，并采用适当的控温措施促进磁铁矿相晶粒长大。处理后，铜渣中磁铁矿的富集度从22％提高到85％以上。控制5K／min的降温速率，磁铁矿平均粒度可达到80-95μm，为磁选分离磁铁矿创造了条件。
通过向熔融的铜渣中鼓入空气或纯氧气的方法研究了铜渣氧化的动力学过程。依据Fe~(2+)的含量变化与反应时间的关系，建立了熔渣动态氧化的表观速率方程，推算出氧化反应的表观活化能。
研究结果表明：纯氧氧化时反应的表观活化能约为296.70kJ／mol，氧化反应的表观速率方程：
Ink_(Fe~(2+))=-((296670)／(RT))+18.63；
当空气氧化时表观活化能为340.300kJ／mol，氧化反应的表观速率方程：
Ink_(Fe~(2+))=-((340300)／(RT))+22.33；
实验结果表明：铜渣中铁的氧化为一级反应，是高温多相反应。在熔渣等温氧化过程中，Fe~(3+)含量迅速增加并以Fe_3O_4形式首先析出，氧化处理后，渣中铁橄榄石相减少，磁铁矿相增加，实现了铁组分向磁铁矿相的富集。
氧化过程中，渣中FeO含量降低，Si-O络离子团聚合成长链的阴离子，磁铁矿晶体的不断析出和生长，使熔渣的黏度随X_(Fe~(3+))／X_(Fe~(2+))的比值增加而增大。
论文研究了等温和非等温(降温)过程渣中磁铁矿晶粒的析出和生长行为。
实验结果表明：等温过程中，磁铁矿相的相对转变分数x可用经典的Avrami方程描述：
x=1-exp(-kt~n)，
在1473-1573K范围内，X_(Fe~(3+))／X_(Fe~(2+))=1／4时，n=2.0左右，
Dump slags from copper smelting prove to be a valuable source of base and rare metals. A typical copper slag may have the composition of 40-50wt% iron, which is much higher than the 29.1wt% average ore grade for iron smelting. Recovery those iron constituents are important from both economical and environmental perspective. However, due to fine mineral dissemination and complex mineralogy, while iron mainly exists in the form of fayalite(Fe_2SiO_4), Recovery those valuable constituents in slag is a very meaningful task by traditional approachs.
Based on the study of copper slags composition feature, concentrated iron into magnetite(Fe_3O_4) phase by selected oxidizing molten slag by air(or oxygen). As a result, the average grain size of magnetite particles grow from 25μm to 95μm and the iron enrichment in magnetite phase rised from 22% to 86% with cooling rate 5K/min after oxidizing. All those pave a way for magnetic separating the magnetite phase in copper slags.
Oxidization kinetic in copper slag was investigated by blowing oxygen (or air) into molten slag. Based on the relationship between content of the Fe~(2+) and oxidizing time in different temperature, oxidizing kinetic equations were established, from which the apparent energetic E_α of those reactions were also deduced.
The results show that while oxidizing by pure oxygen, apparent energetic E_α is 296.70kJ/mol, reaction rate equation expressed as:
While oxidizing by air, E_α=340.30kJ/mol, reaction rate equation expressed as:
The results show that ferrous oxidizing in slag is a first order heterophase reaction. In isothermal oxidizing process, content of Fe~(3+) increase rapidly, become saturation and firstly precipitate in the form of Fe_3O_4. Main phases in the slag after cooling down were magnetite (Fe_3O_4), fayalite(Fe_2SiO_4) and glass state silicate ((Fe, Ca)SiO_4). In oxidizing
本文基于铜渣的特点，通过对熔融铜渣的氧化处理，实现渣中铁组分向磁铁矿相选择性富集，并采用适当的控温措施促进磁铁矿相晶粒长大。处理后，铜渣中磁铁矿的富集度从22％提高到85％以上。控制5K／min的降温速率，磁铁矿平均粒度可达到80-95μm，为磁选分离磁铁矿创造了条件。
通过向熔融的铜渣中鼓入空气或纯氧气的方法研究了铜渣氧化的动力学过程。依据Fe~(2+)的含量变化与反应时间的关系，建立了熔渣动态氧化的表观速率方程，推算出氧化反应的表观活化能。
研究结果表明：纯氧氧化时反应的表观活化能约为296.70kJ／mol，氧化反应的表观速率方程：
Ink_(Fe~(2+))=-((296670)／(RT))+18.63；
当空气氧化时表观活化能为340.300kJ／mol，氧化反应的表观速率方程：
Ink_(Fe~(2+))=-((340300)／(RT))+22.33；
实验结果表明：铜渣中铁的氧化为一级反应，是高温多相反应。在熔渣等温氧化过程中，Fe~(3+)含量迅速增加并以Fe_3O_4形式首先析出，氧化处理后，渣中铁橄榄石相减少，磁铁矿相增加，实现了铁组分向磁铁矿相的富集。
氧化过程中，渣中FeO含量降低，Si-O络离子团聚合成长链的阴离子，磁铁矿晶体的不断析出和生长，使熔渣的黏度随X_(Fe~(3+))／X_(Fe~(2+))的比值增加而增大。
论文研究了等温和非等温(降温)过程渣中磁铁矿晶粒的析出和生长行为。
实验结果表明：等温过程中，磁铁矿相的相对转变分数x可用经典的Avrami方程描述：
x=1-exp(-kt~n)，
在1473-1573K范围内，X_(Fe~(3+))／X_(Fe~(2+))=1／4时，n=2.0左右，
Dump slags from copper smelting prove to be a valuable source of base and rare metals. A typical copper slag may have the composition of 40-50wt% iron, which is much higher than the 29.1wt% average ore grade for iron smelting. Recovery those iron constituents are important from both economical and environmental perspective. However, due to fine mineral dissemination and complex mineralogy, while iron mainly exists in the form of fayalite(Fe_2SiO_4), Recovery those valuable constituents in slag is a very meaningful task by traditional approachs.
Based on the study of copper slags composition feature, concentrated iron into magnetite(Fe_3O_4) phase by selected oxidizing molten slag by air(or oxygen). As a result, the average grain size of magnetite particles grow from 25μm to 95μm and the iron enrichment in magnetite phase rised from 22% to 86% with cooling rate 5K/min after oxidizing. All those pave a way for magnetic separating the magnetite phase in copper slags.
Oxidization kinetic in copper slag was investigated by blowing oxygen (or air) into molten slag. Based on the relationship between content of the Fe~(2+) and oxidizing time in different temperature, oxidizing kinetic equations were established, from which the apparent energetic E_α of those reactions were also deduced.
The results show that while oxidizing by pure oxygen, apparent energetic E_α is 296.70kJ/mol, reaction rate equation expressed as:
While oxidizing by air, E_α=340.30kJ/mol, reaction rate equation expressed as:
The results show that ferrous oxidizing in slag is a first order heterophase reaction. In isothermal oxidizing process, content of Fe~(3+) increase rapidly, become saturation and firstly precipitate in the form of Fe_3O_4. Main phases in the slag after cooling down were magnetite (Fe_3O_4), fayalite(Fe_2SiO_4) and glass state silicate ((Fe, Ca)SiO_4). In oxidizing
引文
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