低品位镍红土矿湿法冶金提取基础理论及工艺研究
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摘要
镍是一种重要的有色金属,广泛应用于不锈钢、高温合金、电池材料以及各种化工产品中。近年来,在全球镍消费持续下跌的情况下,我国镍消费仍以每年25%左右的速度增长,已成为全球最大的镍消费国。世界陆地镍资源中有72%储存在镍红土矿中,但其镍产量仅占全球镍产量的42%。随着镍硫化矿的逐渐枯竭,镍红土矿已经成为全球镍资源开发的重点。湿法冶金处理镍红土矿工艺具有有价金属回收率高、选择性好、能耗低、目标金属产品类型多等优点,已成为低品位镍红土矿处理的主要工艺流程。本论文针对国内外三个不同矿区低品位褐铁矿型镍红土矿的性质和特点,开展镍红土矿湿法冶金处理基础理论和工艺研究,为低品位镍红土矿的工业技术开发提供理论和技术依据。
通过对国内外不同地区的低品位褐铁矿型镍红土矿化学成分、物相结构和元素赋存状态的分析,确定了适合的湿法处理工艺。青海元石山地区低品位镍红土矿中主要物相为针铁矿,镍和钻主要以晶格取代的形式存在于针铁矿中,且钴含量极低,选择采用还原焙烧-氨浸工艺处理；菲律宾Tubay地区低品位镍红土矿中主要物相为针铁矿,钴含量相对较高,具有回收价值,且主要以物理吸附的形式存在于氧化锰颗粒中,选择硫酸熟化焙烧-浸出工艺处理；菲律宾Mati地区低品位镍红土矿中的物相包括针铁矿、磁铁矿、蛇纹石和滑石,镁含量相对较高,镍主要以晶格取代的形式存在于针铁矿中,钴主要以吸附形式存在于氧化锰颗粒中,镁主要以非晶形和弱晶型镁矿物存在,选择常压盐酸浸出工艺处理。
系统研究了镍红土矿还原焙烧-氨浸过程基础理论及工艺过程。热力学分析表明,还原焙烧过程可以将镍红土矿中绝大部分镍、钴氧化物被还原为金属态,同时使大部分的铁转化为Fe3O4；控制一定的氨浸条件,Ni、Co能以稳定氨配合物的形式溶出,Fe以Fe(OH)3沉淀形式进入渣中。确定了还原焙烧-氨浸过程的适宜工艺条件：原料粒度<20目,还原剂用量20wt.%,焙烧温度850℃,焙烧时间30min,氨浸温度40℃,氨浸时间10min,NH3/CO2=133:88,矿浆浓度70g/L通氧速率为0.1L/(min-g)。在此条件下,Ni、Co、Fe浸出率分别为83.1%、45.1%和0.12%,浸出液中Ni/Fe达到45.9,实现了Ni的选择性浸出。对还原焙烧过程进行了优化实验设计,结果表明：响应曲面设计有效地模拟了Co的浸出行为,确定了优化条件为还原剂用量20wt.%、焙烧温度930℃和焙烧时间30mmin,但在模拟Ni的浸出行为过程中出现了数据失真。研究了氨浸过程中Ni、Co的浸出动力学,结果表明：Ni、Co的浸出行为符合多相液固区域反应动力学模型,Ni、Co浸出反应表观活化能分别为18.07kJ/mol和8.99kJ/mol,均为固膜扩散控制过程。
系统研究了镍红土矿硫酸熟化焙烧-浸出过程基础理论及工艺过程,分别采用了硫酸熟化焙烧-水浸和硫酸熟化焙烧-氨浸两种方法处理镍红土矿。热力学分析表明,镍红土矿中所有形式的金属氧化物都可以和浓硫酸反应,生成的硫酸熟化产物经特定温度的焙烧处理,可以将Fe等杂质的硫酸盐分解成相应的氧化物,而Ni、Co等有价金属仍以硫酸盐形式存在,并通过浸出过程实现Ni、Co与Fe等杂质的初步分离；在氨浸过程中,提高总氨浓度有利于提高溶液中镍和钴的离子浓度,C032-的存在对镍离子浓度影响不大,但会较大程度地降低溶液中的钴和锰的离子浓度。确定了硫酸熟化焙烧-水浸的适宜工艺条件：水加入量20wt.%,硫酸加入量40wt.%,焙烧温度700℃,焙烧时间120mmin,原料粒度<80目,硫酸钠加入量4wt.%,矿浆浓度1kg/L。在此条件下,Ni、Co、Fe和Mn浸出率分别为83.3%、92.8%、0.8%和94.3%,工艺实现了Ni、Co对Fe的选择性浸出。浸出渣主要成分为Fe203,达到H62级赤铁精矿的品位和化学成分要求。确定了硫酸熟化焙烧-氨浸的适宜工艺条件：水加入量20wt.%,硫酸加入量40wt.%,焙烧温度700℃,焙烧时间30min,原料粒度<80目,硫酸钠加入量4wt.%,氨浓度为5mol/L,碳酸铵浓度1mol/L,矿浆浓度300g/L,氨浸温度25℃,氨浸时间为10min。在此条件下,Ni、Co、Fe、Mn浸出率分别为82.5%、61.0%、0.007%和22.1%。对硫酸熟化焙烧过程进行了优化实验设计,绘制了Ni、Fe浸出率等值线叠加图,确定了Ni%≥80%&Fe%≤5%的目标优化区域,对区域内条件点的验证实验表明实验数据与理论预测值非常吻合,说明采用响应曲面设计模拟硫酸熟化焙烧过程是非常成功的。研究了硫酸熟化焙烧过程中Ni、Co的硫酸化动力学,结果表明：Ni、Co的硫酸化反应的表观活化能分别为21.45kJ/mol和34.81kJ/mol,反应速率常数分别为1.05和1.09,均为固膜扩散控制过程。
系统研究了镍红土矿常压盐酸浸出过程基础理论及工艺过程。热力学分析表明,升高温度不利于各物相与盐酸反应的进行,且常压下FeOOH和Fe203不能溶解于盐酸。确定了常压盐酸浸出的适宜工艺条件：酸料比3：1,浸出温度80℃,浸出时间1h,矿浆浓度400g/L,原料粒度<80目,不添加氯化盐。在此条件下,获得Ni、Co、Mg、Fe、Mn浸出率分别为82.5%、70.3%、63.8%、63.7%和80.0%。浸出渣中仍存在针铁矿、磁铁矿、蛇纹石和滑石成分,但渣中蛇纹石和滑石含量相对原矿降低。研究了常压盐酸浸出过程中Ni、Co、Fe的浸出动力学。实验结果表明：Ni、Co、Fe浸出反应的表观活化能分别为71.64kJ/mol、68.73kJ/mol和98.52kJ/mol,均为表面化学反应控制过程。Ⅲ
Nickel, one kind of important nonferrous metal, is widely used in the fields of stainless steel, heat-resistant alloys, batteries and various chemical products. In recent years, with the continuous decrease of nickel consumption in the world, the nickel consumption in China increased by25%average every year, which makes China's nickel consumption rank first in the world.72%of nickel land-based resources in the world are reserved in nickel laterite, which only produce42%of nickel total output. As the depletion of nickel sulfide, nickel laterite is becoming the significant nickel resource in the world. Hydrometallurgical processes have many advantages including high recovery of valuable metals, excellent selectivity, low energy consumption, variety of products and so on, which are the main treatments for nickel laterite. In the paper, based on the analysis of mineral properties and characteristics, fundamental and technological study on treatment of low-grade limonitic nickel laterite from three different mine areas at home and abroad by hydrometallurgical processes were studied, which provide the theoretical and technological basis for the industrial processing of nickel laterite.
Hydrometallurgical processes were distributed to nickel laterite from three different mine areas at home and abroad, based on the analysis of chemical composition, phase and mode of occurrence of element. For the limonitic nickel laterite from Qinghai Yuanshi Moutain area in China, the main phase is goethite, and cobalt content is extremely low. Nickel and cobalt exist in goethite in the form of lattice replacement. This ore was treated by reduction roasting-ammoniacal leaching process. For the limonitic nickel laterite from Tubay area in Philippines, the main phase is goethite, and cobalt content is comparatively high. Cobalt exists in manganese oxide particles in the form of physical adsorption. This ore was treated by sulfation roasting-leaching process. For the limonitic nickel laterite from Mati area in Philippines, the phases are goethite, magnetite, lizardite and talc, and magnesium content is comparatively high. Nickel mainly exists in goethite in the form of lattice replacement, and cobalt mainly exists in manganese oxide particles in adsorption form, and magnesium mainly exists as noncrystallne and weak-crystalline. This ore was treated by atmosphere hydrochloric acid leaching process.
The fundamental and technology on treatment of nickel laterite by reduction roasting-leaching processes were studied. The thermodynamics show that nickel and cobalt oxides in laterite can be reduced to metal forms, and iron oxide can be mostly reduced to Fe3O4. Under certain ammoniacal leaching conditions, nickel and cobalt exist as stable ammonia complex in leaching solution, and Fe enters into residue as Fe(OH)3form. The suitable conditions of reduction roasting-leaching process were determined as follows:less than20mesh of mineral particle size,20wt.%of reductant addition,850℃of roasting temperature,30min of roasting time,40℃of leaching temperature,10min leaching time,133:88of NH3/CO2,70g/L of pulp density and0.1L/(min·g) of oxygen flow rate. Under these conditions, the leaching efficiencies of nickel, cobalt and iron are83.1%,45.1%and0.12%, respectively, and the ratio of nickel to iron is45.9in leaching solution, which shows a selective leaching of nickel over iron. The experimental design for optimization of reduction roasting process was done, and the results show that the leaching behavior of cobalt was effectively simulated by Response Surface Methodology (RSM), and the optimum conditions were dertemined as20wt.%of reductant addition,930℃of roasting temperature and30min of roasting time. However, the data distortion phenomenon appeared in the simulation of nickel in leaching process. The kinetics of leaching of nickel and cobalt were investigated, and the results show that the leaching behavior of nickel and cobalt fit well with the kinetic models of multiphase liquid/solid regional reactions. The apparent activation energies for nickel and cobalt extraction are18.07kJ/mol and8.99kJ/mol, respectively, which indicates that the leaching rate of nickel and cobalt were controlled by solid film diffusion.
The fundamental and technology on treatment of nickel laterite by sulfation roasting-leaching process were studied, in which sulfation roasting-water leaching and sulfation roasting-ammoniacal leaching were used to treat nickel laterite. The thermodynamics indicate that all metal oxides in nickel laterite can react with concentrated sulfuric acid. After roasting process in determined temperature, some sulfates like iron sulfate were transformed to corresponding oxides, but nickel, cobalt and other metals remained as sulfates, which achieved the primary separation of nickel and cobalt from iron and other impurities. In ammoniacal leaching process, the increase of total ammonia concentration is beneficial to the increase of nickel and cobalt concentration, and the existence of CO32-has little effect on nickel ion concentration, but effectively decreases the concentration of cobalt and manganese ions. The suitable conditions of reduction roasting-water leaching process were determined as follows:20wt.%of water addition,40wt.%of sulfuric acid addition,700℃of roasting temperature,120min of roasting time, less than80mesh of mineral particle size,4wt.%of sodium sulfate addition and1kg/L of pulp density. Under these conditions, the leaching efficiencies of nickel, cobalt, iron and manganese are83.3%,92.8%,0.8%and94.3%, respectively, which show selective separation of nickel and cobalt over iron. The leaching residue, whose main phase is Fe2O3, meets the requirement of grade and chemical composition of level H62hematite concentrate. The suitable conditions of reduction roasting-ammoniacal leaching process were determined as follows:20wt.%of water addition,40wt.%of sulfuric acid addition,700℃of roasting temperature,30min of roasting time, less than80mesh of mineral particle size,4wt.%of sodium sulfate addition,5mol/L of ammonia concentration, lmol/L of ammonia carbonate,300g/L of pulp density,25℃of leaching temperature,10min of leaching time. Under these conditions, the leaching efficiencies of nickel, cobalt, iron and manganese are82.5%,61.0%,0.007%and22.1%, respectively. The experimental design for optimization of sulfation roasting process was done, and the overlaid of contour plots of nickel and iron extraction was displayed. The optimum area of Ni%≥80%&Fe%≤5%was determined, and in this area the experimental results show excellent agreement with the predicted ones, which indicates that it is quite successful to simulate the sulfation roasting process by RSM. The kinetics of sulfation of nickel and cobalt were investigated, and the results show that the apparent activation energies for nickel and cobalt sulfation are21.45kJ/mol and34.81kJ/mol, and the reaction rate constants for nickel and cobalt sulfation are1.05and1.09, respectively, which indicates that the sulfation rate of nickel and cobalt were controlled by solid film diffusion.
The fundamental and technology on treatment of nickel laterite by hydrochloric acid leaching process at room temperature were studied. The thermodynamics show that the increase of temperature is beneficial to the reactions in hydrochloric acid leaching, and FeOOH and Fe2O3are stable in hydrochloric acid at atmosphere. The suitable conditions of hydrochloric acid leaching process were determined as follows:3:1of acid to ore ratio,80℃of leaching temperature,1h of leaching time,400g/L of pulp density, less than80mesh of mineral particle size, no addition of chloride. Under these conditions, the leaching efficiencies of nickel, cobalt, magnesium, iron and manganese are82.5%,70.3%,63.8%,63.7%and80.0%, respectively. The leaching residue mainly consists of goethite, magnetite, lizardite and talc, but with lower content of lizardite and talc compared to laterite ore. The kinetics of hydrochloric acid leaching of nickel, cobalt and iron were investigated, and the results show that the apparent activation energies for nickel, cobalt and iron extraction are71.64kJ/mol,68.73kJ/mol and98.52kJ/mol, respectively, which indicates that the leaching rate of nickel, cobalt and iron were controlled by surface chemical reactions.
通过对国内外不同地区的低品位褐铁矿型镍红土矿化学成分、物相结构和元素赋存状态的分析,确定了适合的湿法处理工艺。青海元石山地区低品位镍红土矿中主要物相为针铁矿,镍和钻主要以晶格取代的形式存在于针铁矿中,且钴含量极低,选择采用还原焙烧-氨浸工艺处理；菲律宾Tubay地区低品位镍红土矿中主要物相为针铁矿,钴含量相对较高,具有回收价值,且主要以物理吸附的形式存在于氧化锰颗粒中,选择硫酸熟化焙烧-浸出工艺处理；菲律宾Mati地区低品位镍红土矿中的物相包括针铁矿、磁铁矿、蛇纹石和滑石,镁含量相对较高,镍主要以晶格取代的形式存在于针铁矿中,钴主要以吸附形式存在于氧化锰颗粒中,镁主要以非晶形和弱晶型镁矿物存在,选择常压盐酸浸出工艺处理。
系统研究了镍红土矿还原焙烧-氨浸过程基础理论及工艺过程。热力学分析表明,还原焙烧过程可以将镍红土矿中绝大部分镍、钴氧化物被还原为金属态,同时使大部分的铁转化为Fe3O4；控制一定的氨浸条件,Ni、Co能以稳定氨配合物的形式溶出,Fe以Fe(OH)3沉淀形式进入渣中。确定了还原焙烧-氨浸过程的适宜工艺条件：原料粒度<20目,还原剂用量20wt.%,焙烧温度850℃,焙烧时间30min,氨浸温度40℃,氨浸时间10min,NH3/CO2=133:88,矿浆浓度70g/L通氧速率为0.1L/(min-g)。在此条件下,Ni、Co、Fe浸出率分别为83.1%、45.1%和0.12%,浸出液中Ni/Fe达到45.9,实现了Ni的选择性浸出。对还原焙烧过程进行了优化实验设计,结果表明：响应曲面设计有效地模拟了Co的浸出行为,确定了优化条件为还原剂用量20wt.%、焙烧温度930℃和焙烧时间30mmin,但在模拟Ni的浸出行为过程中出现了数据失真。研究了氨浸过程中Ni、Co的浸出动力学,结果表明：Ni、Co的浸出行为符合多相液固区域反应动力学模型,Ni、Co浸出反应表观活化能分别为18.07kJ/mol和8.99kJ/mol,均为固膜扩散控制过程。
系统研究了镍红土矿硫酸熟化焙烧-浸出过程基础理论及工艺过程,分别采用了硫酸熟化焙烧-水浸和硫酸熟化焙烧-氨浸两种方法处理镍红土矿。热力学分析表明,镍红土矿中所有形式的金属氧化物都可以和浓硫酸反应,生成的硫酸熟化产物经特定温度的焙烧处理,可以将Fe等杂质的硫酸盐分解成相应的氧化物,而Ni、Co等有价金属仍以硫酸盐形式存在,并通过浸出过程实现Ni、Co与Fe等杂质的初步分离；在氨浸过程中,提高总氨浓度有利于提高溶液中镍和钴的离子浓度,C032-的存在对镍离子浓度影响不大,但会较大程度地降低溶液中的钴和锰的离子浓度。确定了硫酸熟化焙烧-水浸的适宜工艺条件：水加入量20wt.%,硫酸加入量40wt.%,焙烧温度700℃,焙烧时间120mmin,原料粒度<80目,硫酸钠加入量4wt.%,矿浆浓度1kg/L。在此条件下,Ni、Co、Fe和Mn浸出率分别为83.3%、92.8%、0.8%和94.3%,工艺实现了Ni、Co对Fe的选择性浸出。浸出渣主要成分为Fe203,达到H62级赤铁精矿的品位和化学成分要求。确定了硫酸熟化焙烧-氨浸的适宜工艺条件：水加入量20wt.%,硫酸加入量40wt.%,焙烧温度700℃,焙烧时间30min,原料粒度<80目,硫酸钠加入量4wt.%,氨浓度为5mol/L,碳酸铵浓度1mol/L,矿浆浓度300g/L,氨浸温度25℃,氨浸时间为10min。在此条件下,Ni、Co、Fe、Mn浸出率分别为82.5%、61.0%、0.007%和22.1%。对硫酸熟化焙烧过程进行了优化实验设计,绘制了Ni、Fe浸出率等值线叠加图,确定了Ni%≥80%&Fe%≤5%的目标优化区域,对区域内条件点的验证实验表明实验数据与理论预测值非常吻合,说明采用响应曲面设计模拟硫酸熟化焙烧过程是非常成功的。研究了硫酸熟化焙烧过程中Ni、Co的硫酸化动力学,结果表明：Ni、Co的硫酸化反应的表观活化能分别为21.45kJ/mol和34.81kJ/mol,反应速率常数分别为1.05和1.09,均为固膜扩散控制过程。
系统研究了镍红土矿常压盐酸浸出过程基础理论及工艺过程。热力学分析表明,升高温度不利于各物相与盐酸反应的进行,且常压下FeOOH和Fe203不能溶解于盐酸。确定了常压盐酸浸出的适宜工艺条件：酸料比3：1,浸出温度80℃,浸出时间1h,矿浆浓度400g/L,原料粒度<80目,不添加氯化盐。在此条件下,获得Ni、Co、Mg、Fe、Mn浸出率分别为82.5%、70.3%、63.8%、63.7%和80.0%。浸出渣中仍存在针铁矿、磁铁矿、蛇纹石和滑石成分,但渣中蛇纹石和滑石含量相对原矿降低。研究了常压盐酸浸出过程中Ni、Co、Fe的浸出动力学。实验结果表明：Ni、Co、Fe浸出反应的表观活化能分别为71.64kJ/mol、68.73kJ/mol和98.52kJ/mol,均为表面化学反应控制过程。Ⅲ
Nickel, one kind of important nonferrous metal, is widely used in the fields of stainless steel, heat-resistant alloys, batteries and various chemical products. In recent years, with the continuous decrease of nickel consumption in the world, the nickel consumption in China increased by25%average every year, which makes China's nickel consumption rank first in the world.72%of nickel land-based resources in the world are reserved in nickel laterite, which only produce42%of nickel total output. As the depletion of nickel sulfide, nickel laterite is becoming the significant nickel resource in the world. Hydrometallurgical processes have many advantages including high recovery of valuable metals, excellent selectivity, low energy consumption, variety of products and so on, which are the main treatments for nickel laterite. In the paper, based on the analysis of mineral properties and characteristics, fundamental and technological study on treatment of low-grade limonitic nickel laterite from three different mine areas at home and abroad by hydrometallurgical processes were studied, which provide the theoretical and technological basis for the industrial processing of nickel laterite.
Hydrometallurgical processes were distributed to nickel laterite from three different mine areas at home and abroad, based on the analysis of chemical composition, phase and mode of occurrence of element. For the limonitic nickel laterite from Qinghai Yuanshi Moutain area in China, the main phase is goethite, and cobalt content is extremely low. Nickel and cobalt exist in goethite in the form of lattice replacement. This ore was treated by reduction roasting-ammoniacal leaching process. For the limonitic nickel laterite from Tubay area in Philippines, the main phase is goethite, and cobalt content is comparatively high. Cobalt exists in manganese oxide particles in the form of physical adsorption. This ore was treated by sulfation roasting-leaching process. For the limonitic nickel laterite from Mati area in Philippines, the phases are goethite, magnetite, lizardite and talc, and magnesium content is comparatively high. Nickel mainly exists in goethite in the form of lattice replacement, and cobalt mainly exists in manganese oxide particles in adsorption form, and magnesium mainly exists as noncrystallne and weak-crystalline. This ore was treated by atmosphere hydrochloric acid leaching process.
The fundamental and technology on treatment of nickel laterite by reduction roasting-leaching processes were studied. The thermodynamics show that nickel and cobalt oxides in laterite can be reduced to metal forms, and iron oxide can be mostly reduced to Fe3O4. Under certain ammoniacal leaching conditions, nickel and cobalt exist as stable ammonia complex in leaching solution, and Fe enters into residue as Fe(OH)3form. The suitable conditions of reduction roasting-leaching process were determined as follows:less than20mesh of mineral particle size,20wt.%of reductant addition,850℃of roasting temperature,30min of roasting time,40℃of leaching temperature,10min leaching time,133:88of NH3/CO2,70g/L of pulp density and0.1L/(min·g) of oxygen flow rate. Under these conditions, the leaching efficiencies of nickel, cobalt and iron are83.1%,45.1%and0.12%, respectively, and the ratio of nickel to iron is45.9in leaching solution, which shows a selective leaching of nickel over iron. The experimental design for optimization of reduction roasting process was done, and the results show that the leaching behavior of cobalt was effectively simulated by Response Surface Methodology (RSM), and the optimum conditions were dertemined as20wt.%of reductant addition,930℃of roasting temperature and30min of roasting time. However, the data distortion phenomenon appeared in the simulation of nickel in leaching process. The kinetics of leaching of nickel and cobalt were investigated, and the results show that the leaching behavior of nickel and cobalt fit well with the kinetic models of multiphase liquid/solid regional reactions. The apparent activation energies for nickel and cobalt extraction are18.07kJ/mol and8.99kJ/mol, respectively, which indicates that the leaching rate of nickel and cobalt were controlled by solid film diffusion.
The fundamental and technology on treatment of nickel laterite by sulfation roasting-leaching process were studied, in which sulfation roasting-water leaching and sulfation roasting-ammoniacal leaching were used to treat nickel laterite. The thermodynamics indicate that all metal oxides in nickel laterite can react with concentrated sulfuric acid. After roasting process in determined temperature, some sulfates like iron sulfate were transformed to corresponding oxides, but nickel, cobalt and other metals remained as sulfates, which achieved the primary separation of nickel and cobalt from iron and other impurities. In ammoniacal leaching process, the increase of total ammonia concentration is beneficial to the increase of nickel and cobalt concentration, and the existence of CO32-has little effect on nickel ion concentration, but effectively decreases the concentration of cobalt and manganese ions. The suitable conditions of reduction roasting-water leaching process were determined as follows:20wt.%of water addition,40wt.%of sulfuric acid addition,700℃of roasting temperature,120min of roasting time, less than80mesh of mineral particle size,4wt.%of sodium sulfate addition and1kg/L of pulp density. Under these conditions, the leaching efficiencies of nickel, cobalt, iron and manganese are83.3%,92.8%,0.8%and94.3%, respectively, which show selective separation of nickel and cobalt over iron. The leaching residue, whose main phase is Fe2O3, meets the requirement of grade and chemical composition of level H62hematite concentrate. The suitable conditions of reduction roasting-ammoniacal leaching process were determined as follows:20wt.%of water addition,40wt.%of sulfuric acid addition,700℃of roasting temperature,30min of roasting time, less than80mesh of mineral particle size,4wt.%of sodium sulfate addition,5mol/L of ammonia concentration, lmol/L of ammonia carbonate,300g/L of pulp density,25℃of leaching temperature,10min of leaching time. Under these conditions, the leaching efficiencies of nickel, cobalt, iron and manganese are82.5%,61.0%,0.007%and22.1%, respectively. The experimental design for optimization of sulfation roasting process was done, and the overlaid of contour plots of nickel and iron extraction was displayed. The optimum area of Ni%≥80%&Fe%≤5%was determined, and in this area the experimental results show excellent agreement with the predicted ones, which indicates that it is quite successful to simulate the sulfation roasting process by RSM. The kinetics of sulfation of nickel and cobalt were investigated, and the results show that the apparent activation energies for nickel and cobalt sulfation are21.45kJ/mol and34.81kJ/mol, and the reaction rate constants for nickel and cobalt sulfation are1.05and1.09, respectively, which indicates that the sulfation rate of nickel and cobalt were controlled by solid film diffusion.
The fundamental and technology on treatment of nickel laterite by hydrochloric acid leaching process at room temperature were studied. The thermodynamics show that the increase of temperature is beneficial to the reactions in hydrochloric acid leaching, and FeOOH and Fe2O3are stable in hydrochloric acid at atmosphere. The suitable conditions of hydrochloric acid leaching process were determined as follows:3:1of acid to ore ratio,80℃of leaching temperature,1h of leaching time,400g/L of pulp density, less than80mesh of mineral particle size, no addition of chloride. Under these conditions, the leaching efficiencies of nickel, cobalt, magnesium, iron and manganese are82.5%,70.3%,63.8%,63.7%and80.0%, respectively. The leaching residue mainly consists of goethite, magnetite, lizardite and talc, but with lower content of lizardite and talc compared to laterite ore. The kinetics of hydrochloric acid leaching of nickel, cobalt and iron were investigated, and the results show that the apparent activation energies for nickel, cobalt and iron extraction are71.64kJ/mol,68.73kJ/mol and98.52kJ/mol, respectively, which indicates that the leaching rate of nickel, cobalt and iron were controlled by surface chemical reactions.
引文
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