低品位硫化镍矿中含镍硫化矿物同步疏水的理论与技术研究
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摘要
随着高品位硫化镍矿资源储量的不断减少,对低品位硫化镍矿的开发显得日益重要。低品位硫化镍矿中的镍金属主要以镍黄铁矿的形式存在,但镍黄铁矿与磁黄铁矿和黄铁矿紧密共生且嵌布粒度不均,难以单体解离。为了解决低品位硫化镍矿难以浮选回收的问题,提高镍资源利用率,提出了含镍硫化矿物同步疏水的思想。为实现这一目标,首先针对低品位硫化镍矿中主要的含镍硫化矿物镍黄铁矿、磁黄铁矿和黄铁矿的基本性质从热力学、电化学和第一性原理计算的角度进行了研究,然后考察了浮选矿浆体系中存在的捕收剂、难免金属离子和矿浆调整剂对硫化矿物浮选行为和表面产物的影响。通过以上系统研究,得出了硫化矿物在矿浆中表面产物和疏水性的变化规律,形成了硫化矿物同步疏水调控机制,将之与镁硅酸盐矿物同步分散／抑制理论结合,开发出适合处理低品位硫化镍矿的强化浮选技术。本文的主要研究内容和结论如下：
(1)硫化镍矿中主要硫化矿物的浮选行为及疏水产物
采用热力学、浮选试验、电化学和表面XRD分析等方法研究了硫化矿物在自诱导、硫诱导和捕收剂诱导浮选时表面发生的电化学反应和表面产物,得到了不同条件下硫化矿物的同步疏水pH区间。
根据溶液化学原理,绘制了FeS2-H2O系,FeS-H2O系,(Ni, Fe)9S8-H2O系和NiS-H2O系的Eh-pH图,分析表明,低品位硫化镍矿中的主要硫化矿物均存在适当的Eh, pH区间使矿物表面生成单质硫实现表面疏水；硫化矿物自诱导浮选的主要疏水产物为金属离子溶出后形成的缺金属硫化物和单质硫S0；硫诱导浮选的主要疏水产物为溶液中HS-被氧化吸附在矿物表面的单质硫S0；黄药类捕收剂在硫化矿物表面的主要疏水产物为双黄药；三种硫化矿物在自诱导浮选中的同步疏水区间为：4 采用基于密度泛函的第一性原理对几种镍铁硫化矿物的电子结构进行计算,得到硫化矿物的导电类型和表面活性质点并讨论其对矿物浮选行为的影响。
能带结构分析表明：黄铁矿和针镍矿属于直接带隙p型半导体,镍黄铁矿和磁黄铁矿为金属导体。p型半导体导带电子少容易接收捕收剂的电子,因此捕收剂更容易与黄铁矿作用,而镍黄铁矿和磁黄铁矿为金属导体,与捕收剂作用能力相近；态密度和分态密度分析表明：在所研究的几种镍铁硫化矿物中铁原子的活性最强,镍原子活性次之,因此镍铁硫化矿物中铁原子优先溶出,且表面活性质点的差异导致矿物浮选行为的差异。
(3)硫化镍矿矿浆中主要的难免金属离子及其对硫化矿物腐蚀电化学行为的影响
通过对矿浆溶液的分析确定了硫化镍矿浮选矿浆体系中存在的主要难免金属离子,并用静电位、Tafel极化曲线、循环伏安法和交流阻抗等方法研究了其对矿物腐蚀行为的影响。
硫化镍矿浮选矿浆中存在以Mg2+、Ni2+、Fe3+和Cu2+为主的难免金属离子,各金属离子均会增大磁黄铁矿与黄铁矿和镍黄铁矿的静电位差,增强电偶腐蚀,增大磁黄铁矿与镍黄铁矿和黄铁矿的表面差异。Mg2+使镍黄铁矿表面腐蚀速率增加,却使磁黄铁矿和黄铁矿腐蚀速率降低；Ni2+在低浓度(<5×10-4mol·L-1)下对三种硫化矿物的表面氧化有较强的抑制作用,在较高浓度(≥1×10-3mol·L-1)下抑制作用减弱；Fe3+能加速硫化矿物表面的氧化,作用较短时间就可使矿物表面生成大量疏水性物质(S0),延长作用时间会使矿物表面的疏水性物质被氧化为亲水性物质,降低矿物表面疏水性；Cu2+通过置换反应在镍黄铁矿表面形成疏水性的CuS使镍黄铁矿表面疏水性增加。
(4)矿浆调整剂对硫化矿物疏水性的影响及硫化矿物同步疏水调控机制
通过考察调整剂对硫化矿物表面润湿性、表面电性、捕收剂吸附量、浮选行为和腐蚀行为的影响,确定了实现硫化矿物同步疏水调控的关键因素。
矿浆调整剂CMC和古尔胶会降低硫化矿物的疏水性和回收率；捕收剂PAX与调整剂CMC和古尔胶在硫化矿物表面发生竞争吸附,优先加入捕收剂可以减弱调整剂对硫化矿物的抑制作用,增加捕收剂在矿物表面的吸附量提高硫化矿物疏水性和回收率。
(5)低品位硫化镍矿强化浮选技术
将硫化矿物同步疏水机理与脉石矿物同步分散／抑制机理结合,提出了低品位硫化镍矿强化浮选技术,针对含镍0.53%,铜0.27%的低品位硫化镍矿进行工业试验,得到镍品位5.68%,铜品位3.14%的铜镍混合精矿,镍和铜的回收率分别为80.23%和88.05%,与该选厂原流程生产指标相比,在原矿镍品位和精矿镍品位相近的情况下,镍和铜的回收率分别提高了3.04%和9.92%。
With the continues decline of high-grade nickel sulphide ore reserves, the development of low-grade nickel sulfide ore becomes increasingly important. In low-grade nickel sulfide ore, nickel is mainly in the form of pentlandite, but the particle size distribution of pentlandite, pyrrhotite and pyrite embedded in close symbiosis and uneven, it is difficult to liberation. To solve the problem in the flotation of low-grade nickel sulfide ore and improve the nickel resource utilization, the synchronous hydrophobic thought was proposed. To achieve this thought, the properties of mainly nickel bearing sulfides pentlandite, pyrrhotite and pyrite were investigated using thermodynamics, electrochemistry, and first-principles calculation, then the influence of collector, inevitable metal ions and pulp regulator on the flotation behavior and surface products was identified. By the above systematic study, the synchronous hydrophobic mechanism was formed, and combined it with the synchronous dispersion/inhibition theory of magnesium silicate minerals, an enhanced low-grade nickel sulfide ore flotation technology was developed. The main contents of this paper and conclusions are as follows:
(1) Flotation behavior and hydrophobic products of sulfide minerals
The surface products and electrochemical reactions on nickel bearing sulfide minerals were studied by thermodynamics, flotation tests, electrochemical and surface analytics, the synchronous hydrophobic pH range was determined.
According to solution chemistry, the FeS2-H2O system, FeS-H2O system,(Ni,Fe)9S8-H2system and NiS-H2O system of Eh-pH diagram were drawn, these diagrams show all investigated sulfide minerals might be hydrophobic at appropriate Eh, pH range by forming elemental sulfur; the mainly hydrophobic products in self-induced flotation are formed by the dissolution of metal ions from the surface, forming a metal-deficient sulfides and elemental sulfur S0; the main hydrophobic surface products in Na2S-induced flotation is S0which is the oxidized product of HS-,the formed S0adsorbed on the mineral surface causes the hydrophobic of sulfide minerals; in xanthate collector-induced flotation, the main hydrophobic product is dixanthogen; at different flotation system, these three sulfide minerals'synchronous hydrophobic range are different, in self-induced flotation, the pH range is4 (2) Electronic structure of nickel-iron sulfide minerals and the effect on the flotation behavior
Using First-principles calculation to investigate the electronic structure of nickel-iron sulfide minerals, the conductivity type of sulfide minerals and surface activity particles of mineral was determined, and the implication on the flotation behavior was discussed.
Pyrite and millerite are direct band gap p-type semiconductor, pentlandite and pyrrhotite is metal conductor. The quantity of electrons in conduction band determines the tendency of collector's adsorption, hence, the collector is likely to adsorb on pyrite, less likely to adsorb on pentlandite and pyrrhotite; density of states and partial density of states analysis showed that Fe atoms is the most active particle in nickel-iron sulfide minerals, followed by Ni atoms, this is the reason why Fe atoms dissolved preferentially from nickel-iron sulphide minerals, and the difference of surface active particle leads to the difference of flotation behavior.
(3) Inevitable metal ions in nickel sulfide pulp and the influence on the corrosion electrochemistry of sulfide minerals
Through the pulp solution analysis, the species of inevitable metal ions were identified, open circuit potential tests, Tafel polarization curves, cyclic voltammetry and AC impedance were used to study their influence on the corrosion behavior of sulfide minerals.
In nickel sulfide flotation pulp, Ni2+, Fe3+, Cu2+, and Mg2+are the main inevitable metal ions, all of them will increase the difference between pyrrhotite and pyrite, pentlandite in electrostatic potential, enhancing galvanic corrosion. Mg2+will increase the corrosion rate of pentlandite, while decrease the corrosion rate of pyrrhotite and pyrite; Ni2+would inhibit the oxidation of sulfide minerals at low concentrations (<5×10-4mol·L-1), increase the Ni2+concentration, the inhibit effect reduced; Fe3+can accelerate the oxidation of sulfide mineral surfaces, mineral surface would generation of large amount of hydrophobic product (S0) in shorter time, extend the duration, the surface hydrophobic substances are further oxidized to hydrophilic products, reduce the hydrophobic of sulfide minerals; Cu2+would be in the form of CuS through displacement reaction at pentlandite surface, increase the hydrophobicity of nickel bearing sulfide mineral.
(4) Effect of pulp regulator on the hydrophobic of sulfide minerals and the synchronous hydrophobic mechanism of sulphide minerals
By investigating the surface wettability, surface potential, collector adsorption amount, flotation behavior and corrosion behavior of sulfide minerals in the presence of pulp regulator, the key factor of synchronous hydrophobic was determined.
Pulp regulator(CMC, gur gum) will reduce the hydrophobicity and flotation recovery of sulfide minerals; the adsorb mechanism of collector(PAX) and pulp regulator(CMC, gur gum) on sulfide mineral surface is competitive adsorption, preferentially adding collector can reduced the inhibition of sulfide minerals by regulators, increasing the adsorption of collector and improve the hydrophobic of sulfide minerals.
(5) Enhanced flotation technology of low-grade nickel sulfide ore
Combining the synchronous hydrophobic mechanism of sulfide minerals and synchronous dispersion/inhabitation mechanism of gangue minerals, the enhanced flotation technology of low-grade nickel sulphide ore was proposed, for the low-grade nickel sulfide ore containing0.68%of Ni, using this new technology, the Ni and Cu grade were6.84%and0.91%in the obtained concentrate, Ni, Cu recovery were81.3%and81.4%. on the basis of ensure the quality of concentrate, largely increase the metal recovery.
(1)硫化镍矿中主要硫化矿物的浮选行为及疏水产物
采用热力学、浮选试验、电化学和表面XRD分析等方法研究了硫化矿物在自诱导、硫诱导和捕收剂诱导浮选时表面发生的电化学反应和表面产物,得到了不同条件下硫化矿物的同步疏水pH区间。
根据溶液化学原理,绘制了FeS2-H2O系,FeS-H2O系,(Ni, Fe)9S8-H2O系和NiS-H2O系的Eh-pH图,分析表明,低品位硫化镍矿中的主要硫化矿物均存在适当的Eh, pH区间使矿物表面生成单质硫实现表面疏水；硫化矿物自诱导浮选的主要疏水产物为金属离子溶出后形成的缺金属硫化物和单质硫S0；硫诱导浮选的主要疏水产物为溶液中HS-被氧化吸附在矿物表面的单质硫S0；黄药类捕收剂在硫化矿物表面的主要疏水产物为双黄药；三种硫化矿物在自诱导浮选中的同步疏水区间为：4
能带结构分析表明：黄铁矿和针镍矿属于直接带隙p型半导体,镍黄铁矿和磁黄铁矿为金属导体。p型半导体导带电子少容易接收捕收剂的电子,因此捕收剂更容易与黄铁矿作用,而镍黄铁矿和磁黄铁矿为金属导体,与捕收剂作用能力相近；态密度和分态密度分析表明：在所研究的几种镍铁硫化矿物中铁原子的活性最强,镍原子活性次之,因此镍铁硫化矿物中铁原子优先溶出,且表面活性质点的差异导致矿物浮选行为的差异。
(3)硫化镍矿矿浆中主要的难免金属离子及其对硫化矿物腐蚀电化学行为的影响
通过对矿浆溶液的分析确定了硫化镍矿浮选矿浆体系中存在的主要难免金属离子,并用静电位、Tafel极化曲线、循环伏安法和交流阻抗等方法研究了其对矿物腐蚀行为的影响。
硫化镍矿浮选矿浆中存在以Mg2+、Ni2+、Fe3+和Cu2+为主的难免金属离子,各金属离子均会增大磁黄铁矿与黄铁矿和镍黄铁矿的静电位差,增强电偶腐蚀,增大磁黄铁矿与镍黄铁矿和黄铁矿的表面差异。Mg2+使镍黄铁矿表面腐蚀速率增加,却使磁黄铁矿和黄铁矿腐蚀速率降低；Ni2+在低浓度(<5×10-4mol·L-1)下对三种硫化矿物的表面氧化有较强的抑制作用,在较高浓度(≥1×10-3mol·L-1)下抑制作用减弱；Fe3+能加速硫化矿物表面的氧化,作用较短时间就可使矿物表面生成大量疏水性物质(S0),延长作用时间会使矿物表面的疏水性物质被氧化为亲水性物质,降低矿物表面疏水性；Cu2+通过置换反应在镍黄铁矿表面形成疏水性的CuS使镍黄铁矿表面疏水性增加。
(4)矿浆调整剂对硫化矿物疏水性的影响及硫化矿物同步疏水调控机制
通过考察调整剂对硫化矿物表面润湿性、表面电性、捕收剂吸附量、浮选行为和腐蚀行为的影响,确定了实现硫化矿物同步疏水调控的关键因素。
矿浆调整剂CMC和古尔胶会降低硫化矿物的疏水性和回收率；捕收剂PAX与调整剂CMC和古尔胶在硫化矿物表面发生竞争吸附,优先加入捕收剂可以减弱调整剂对硫化矿物的抑制作用,增加捕收剂在矿物表面的吸附量提高硫化矿物疏水性和回收率。
(5)低品位硫化镍矿强化浮选技术
将硫化矿物同步疏水机理与脉石矿物同步分散／抑制机理结合,提出了低品位硫化镍矿强化浮选技术,针对含镍0.53%,铜0.27%的低品位硫化镍矿进行工业试验,得到镍品位5.68%,铜品位3.14%的铜镍混合精矿,镍和铜的回收率分别为80.23%和88.05%,与该选厂原流程生产指标相比,在原矿镍品位和精矿镍品位相近的情况下,镍和铜的回收率分别提高了3.04%和9.92%。
With the continues decline of high-grade nickel sulphide ore reserves, the development of low-grade nickel sulfide ore becomes increasingly important. In low-grade nickel sulfide ore, nickel is mainly in the form of pentlandite, but the particle size distribution of pentlandite, pyrrhotite and pyrite embedded in close symbiosis and uneven, it is difficult to liberation. To solve the problem in the flotation of low-grade nickel sulfide ore and improve the nickel resource utilization, the synchronous hydrophobic thought was proposed. To achieve this thought, the properties of mainly nickel bearing sulfides pentlandite, pyrrhotite and pyrite were investigated using thermodynamics, electrochemistry, and first-principles calculation, then the influence of collector, inevitable metal ions and pulp regulator on the flotation behavior and surface products was identified. By the above systematic study, the synchronous hydrophobic mechanism was formed, and combined it with the synchronous dispersion/inhibition theory of magnesium silicate minerals, an enhanced low-grade nickel sulfide ore flotation technology was developed. The main contents of this paper and conclusions are as follows:
(1) Flotation behavior and hydrophobic products of sulfide minerals
The surface products and electrochemical reactions on nickel bearing sulfide minerals were studied by thermodynamics, flotation tests, electrochemical and surface analytics, the synchronous hydrophobic pH range was determined.
According to solution chemistry, the FeS2-H2O system, FeS-H2O system,(Ni,Fe)9S8-H2system and NiS-H2O system of Eh-pH diagram were drawn, these diagrams show all investigated sulfide minerals might be hydrophobic at appropriate Eh, pH range by forming elemental sulfur; the mainly hydrophobic products in self-induced flotation are formed by the dissolution of metal ions from the surface, forming a metal-deficient sulfides and elemental sulfur S0; the main hydrophobic surface products in Na2S-induced flotation is S0which is the oxidized product of HS-,the formed S0adsorbed on the mineral surface causes the hydrophobic of sulfide minerals; in xanthate collector-induced flotation, the main hydrophobic product is dixanthogen; at different flotation system, these three sulfide minerals'synchronous hydrophobic range are different, in self-induced flotation, the pH range is4
Using First-principles calculation to investigate the electronic structure of nickel-iron sulfide minerals, the conductivity type of sulfide minerals and surface activity particles of mineral was determined, and the implication on the flotation behavior was discussed.
Pyrite and millerite are direct band gap p-type semiconductor, pentlandite and pyrrhotite is metal conductor. The quantity of electrons in conduction band determines the tendency of collector's adsorption, hence, the collector is likely to adsorb on pyrite, less likely to adsorb on pentlandite and pyrrhotite; density of states and partial density of states analysis showed that Fe atoms is the most active particle in nickel-iron sulfide minerals, followed by Ni atoms, this is the reason why Fe atoms dissolved preferentially from nickel-iron sulphide minerals, and the difference of surface active particle leads to the difference of flotation behavior.
(3) Inevitable metal ions in nickel sulfide pulp and the influence on the corrosion electrochemistry of sulfide minerals
Through the pulp solution analysis, the species of inevitable metal ions were identified, open circuit potential tests, Tafel polarization curves, cyclic voltammetry and AC impedance were used to study their influence on the corrosion behavior of sulfide minerals.
In nickel sulfide flotation pulp, Ni2+, Fe3+, Cu2+, and Mg2+are the main inevitable metal ions, all of them will increase the difference between pyrrhotite and pyrite, pentlandite in electrostatic potential, enhancing galvanic corrosion. Mg2+will increase the corrosion rate of pentlandite, while decrease the corrosion rate of pyrrhotite and pyrite; Ni2+would inhibit the oxidation of sulfide minerals at low concentrations (<5×10-4mol·L-1), increase the Ni2+concentration, the inhibit effect reduced; Fe3+can accelerate the oxidation of sulfide mineral surfaces, mineral surface would generation of large amount of hydrophobic product (S0) in shorter time, extend the duration, the surface hydrophobic substances are further oxidized to hydrophilic products, reduce the hydrophobic of sulfide minerals; Cu2+would be in the form of CuS through displacement reaction at pentlandite surface, increase the hydrophobicity of nickel bearing sulfide mineral.
(4) Effect of pulp regulator on the hydrophobic of sulfide minerals and the synchronous hydrophobic mechanism of sulphide minerals
By investigating the surface wettability, surface potential, collector adsorption amount, flotation behavior and corrosion behavior of sulfide minerals in the presence of pulp regulator, the key factor of synchronous hydrophobic was determined.
Pulp regulator(CMC, gur gum) will reduce the hydrophobicity and flotation recovery of sulfide minerals; the adsorb mechanism of collector(PAX) and pulp regulator(CMC, gur gum) on sulfide mineral surface is competitive adsorption, preferentially adding collector can reduced the inhibition of sulfide minerals by regulators, increasing the adsorption of collector and improve the hydrophobic of sulfide minerals.
(5) Enhanced flotation technology of low-grade nickel sulfide ore
Combining the synchronous hydrophobic mechanism of sulfide minerals and synchronous dispersion/inhabitation mechanism of gangue minerals, the enhanced flotation technology of low-grade nickel sulphide ore was proposed, for the low-grade nickel sulfide ore containing0.68%of Ni, using this new technology, the Ni and Cu grade were6.84%and0.91%in the obtained concentrate, Ni, Cu recovery were81.3%and81.4%. on the basis of ensure the quality of concentrate, largely increase the metal recovery.
引文
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