WO2025020124A1 - Oxygen pressure leaching method for low-grade nickel matte mixed with laterite-nickel ore - Google Patents
Oxygen pressure leaching method for low-grade nickel matte mixed with laterite-nickel ore Download PDFInfo
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- the invention belongs to the field of metallurgy, and in particular relates to an oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore.
- Laterite nickel ore has gradually become the main source of nickel metal.
- the processing technology of laterite nickel ore can be divided into pyrometallurgical process and wet process.
- the wet process includes high-pressure acid leaching and reduction roasting-ammonia leaching, as well as processes such as atmospheric pressure acid leaching and heap leaching that have emerged in recent years.
- the process conditions of high-pressure acid leaching of laterite nickel ore are 255-260°C and 5-6Mpa. It is necessary to add sulfuric acid. Generally, the acid-ore ratio is about 0.3 (concentrated sulfuric acid dosage: 1 ton of dry ore).
- the pressure and temperature of the entire leaching process are high, and the steam energy consumption and equipment performance parameters have high requirements. If the temperature and pressure of high-pressure acid leaching of laterite nickel ore can be reduced, the cost can also be reduced and the loss of equipment can be slowed down.
- low-grade nickel matte is mainly composed of nickel-iron alloy phase.
- the laterite nickel ore is mixed with carbon powder and heated and roasted in a rotary kiln to convert the metal oxides in the original ore into metal elements, forming an intermediate nickel-iron alloy (low-grade nickel matte).
- the production line will be further heated in an electric furnace to remove impurities at around 1500°C, thereby forming high-grade nickel matte. A lot of energy is consumed in this process, and a large amount of Ni and Co are lost. If low-grade nickel matte can be used as raw material for processing, the loss of nickel and cobalt can be avoided and energy consumption can be reduced.
- an object of the present invention is to provide an oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore.
- An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
- the raw laterite nickel ore is pretreated to obtain laterite nickel ore pulp; then the pretreated low nickel matte and laterite nickel ore pulp are mixed in a mass ratio of 2:1-6, and sulfuric acid solution is added to carry out oxygen pressure leaching reaction, and the reaction temperature is controlled to be 180-220°C, the pressure is 2.5-3.5Mpa, and the oxygen partial pressure is 20-30%;
- the laterite nickel ore in step (1) is pretreated for mineral processing in the following manner: the laterite nickel ore is washed and then sieved, the -200 mesh slurry enters the finished product tank, the +200 mesh large particle ore is processed by a spiral chute and a shaking table once to remove the chromite contained therein, and the tailings are placed in a ball mill, wet-milled for 5 minutes under the condition of a steel ball filling ratio of 50%, and then passed through a -200 mesh sieve and enter the finished product tank to form a laterite nickel ore slurry together, and after flocculant concentration and sedimentation, a laterite nickel ore slurry with a slurry concentration of 28-37% is obtained.
- the pretreatment method of the nickel matte in step (1) is: the nickel matte is ball milled for 2 to 4 hours, wherein the water content is 50%, and the nickel matte is ground to 50 to 200 mesh.
- the concentration of the sulfuric acid solution in step (1) is 98 wt %.
- the ratio of the sulfuric acid solution in step (1) to the total mass of the pretreated low-matte nickel and laterite nickel ore slurry is 0.1 to 0.3:1.
- the oxygen pressure leaching reaction time in step (1) is 3 to 8 hours.
- the filtration in step (2) is pressure filtration
- the slag phase of the pressure filtration is mainly composed of Fe 2 O 3 , and also contains Al 2 O 3 , acid-insoluble silicates, and Ni ⁇ 0.05%.
- the method of adjusting the pH of the filtrate in step (2) is to add at least one of limestone and lime milk to adjust the pH.
- reaction process or mechanism involved in the present invention is:
- nickel matte Since the main component of nickel matte is nickel-iron alloy (Fe accounts for 45-60%, Ni accounts for 15-20%), after sulfuric acid is added, it first reacts with Fe to produce FeSO4 , then oxidizes to Fe3 + in an oxygen atmosphere, and then hydrolyzes to Fe2O3 and enters the slag phase, while releasing sulfuric acid to continue dissolving the metal oxides in nickel matte and laterite nickel ore.
- nickel matte also contains a lot of sulfur, which can also generate sulfuric acid under oxygen pressure conditions, which can effectively reduce the additional amount of sulfuric acid added.
- the beneficial effects of the present invention include:
- the present invention adopts the same process production line for high-pressure leaching of laterite nickel ore to simultaneously process low-grade nickel matte and laterite nickel ore, thereby reducing the reaction pressure and reaction temperature of the autoclave and reducing energy consumption.
- Fe 2+ in the leaching system can reduce the presence of Cr 6+ in the laterite nickel ore leaching solution without the need for adding reducing agents.
- FIG1 is a flow chart of an oxygen pressure leaching method for low-matte nickel mixed laterite nickel ore according to the present invention.
- composition of the low-matte nickel used in the embodiments and comparative examples is: Ni content 15-25%, Fe content 45-60%, Co content 0.1%, and S content 8-15%.
- the composition of the laterite nickel ore is as follows: Ni content is 1.1-1.3%, Co content is 0.08-0.1%, Mn content is 1-3%, Fe content is 38-44%, Al content is 2-3%, and Mg content is about 2%.
- the concentration of the sulfuric acid solution is 98 wt %.
- the method for the beneficiation pretreatment of the laterite nickel ore is as follows:
- the laterite nickel ore is washed and sieved, and the -200 mesh slurry enters the finished product tank.
- the +200 mesh large-particle ore is processed by a spiral chute and a shaking table to remove the chromite contained therein.
- the tailings are placed in a ball mill, wet-milled for 5 minutes under the condition of a steel ball filling ratio of 50%, and then passed through a -200 mesh sieve and enter the finished product tank to form a laterite nickel ore slurry. After flocculant concentration and sedimentation, a laterite nickel ore slurry with a slurry concentration of 28-37% is obtained.
- the pretreatment method of the low-matte nickel is: grinding the low-matte nickel to 200 meshes.
- An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
- the raw laterite nickel ore is pretreated to obtain laterite nickel ore pulp; then 200 g of the pretreated low-grade nickel matte and 400 g of the laterite nickel ore pulp are mixed in a mass ratio of 1:2, and 60 g of sulfuric acid solution is added to carry out oxygen pressure leaching reaction, wherein the ratio of the sulfuric acid solution to the total mass of the pretreated low-grade nickel matte and the laterite nickel ore pulp is 0.1:1 (i.e., the acid-ore ratio is 0.1).
- the reaction temperature was controlled at 220°C, the pressure was 3.5 MPa, and the oxygen partial pressure was 30%;
- the pH of the leaching solution is between 0.1 and 0.9, the Ni concentration in the solution is >20g/L, Co>0.5g/L, Fe ⁇ 2g/L, Al ⁇ 1.5g/L; the Ni content in the slag phase is ⁇ 0.08%.
- the acid-ore ratio is reduced to 0.1 during the whole process, which significantly reduces the amount of sulfuric acid used.
- An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
- the ratio of low-matte nickel to laterite nickel ore slurry in step 1 is 1:3, that is, 200g of pretreated low-matte nickel and 600g of laterite nickel ore slurry, and other conditions are the same as in Example 1.
- the pH in the leaching solution rises to 1.1, the content of Ni in the leaching solution is >17g/L, Co>0.4g/L, Fe ⁇ 2g/L, Al ⁇ 1.5g/L; the content of Ni in the slag phase is ⁇ 1.2%.
- the reduction of low-grade nickel matte content will result in an acid-ore ratio of 0.1 being insufficient to dissolve all Ni, so the acid-ore ratio needs to be increased to increase the leaching rate of Ni and Co.
- An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
- the oxygen partial pressure was reduced to 20%, and other conditions remained unchanged.
- the role of oxygen in the autoclave is to oxidize ferrous iron, and at the same time combine with sulfur in the low nickel matte and the H2 produced by the reaction to release heat.
- the oxygen partial pressure drops to 20%
- the Fe content in the leaching solution increases by ⁇ 4.2g/L
- the Ni and Co contents both decrease, Ni ⁇ 15g/L, Co ⁇ 0.35g/L
- the residual Ni and Co in the slag phase also increases. This is mainly due to the decrease in O2 content, which leads to the inability of Fe2 + to be completely oxidized, the reduction in acidity, and the inability to completely dissolve Ni and Co.
- An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
- the reaction time of the oxygen pressure reaction was 2 h, and other conditions remained unchanged.
- the Fe content in the leaching solution is >15g/L, Ni ⁇ 10g/L, Co ⁇ 0.2g/L, and Al ⁇ 4g/L. Insufficient reaction time results in the incomplete conversion of Fe 3+ and a decrease in the leaching rate.
- An oxygen pressure leaching method for laterite nickel ore the steps are as follows:
- step (1) no low-matte nickel is added, and the leaching effect of laterite nickel ore under the same conditions is compared.
- a method for preparing a nickel-cobalt-manganese sulfate solution comprising the following steps:
- step (2) no limestone is added to the leachate to adjust the pH and remove iron and aluminum impurities, and the extraction is carried out directly, while other conditions remain unchanged.
- the high content of Fe and Al in the leachate has a significant impact on the selective extraction of Ni by the extractant Versatic 10.
- the Ni extraction rate is reduced from 98% to 64%.
- the Fe and Al entering the loaded organic phase affect the reuse performance of the extractant.
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Abstract
Description
本发明属于冶金领域，尤其涉及一种低冰镍混合红土镍矿的氧压浸出方法。The invention belongs to the field of metallurgy, and in particular relates to an oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore.
红土镍矿逐渐成为镍金属的主要来源，红土镍矿的处理工艺可分为火法工艺和湿法工艺。其中，湿法工艺包括高压酸浸和还原焙烧-氨浸以及近年来出现的如常压酸浸、堆浸等工艺。红土镍矿高压酸浸工艺条件为255～260℃，压力5～6Mpa条件下浸出，需要额外加入硫酸，一般酸矿比0.3左右(浓硫酸用量：1吨干矿)。整个浸出过程压力和温度较高，蒸汽能耗，设备性能参数都有较高要求。如果能降低红土镍矿高压酸浸时的温度和压力，也能降低成本，减缓对设备的损耗。Laterite nickel ore has gradually become the main source of nickel metal. The processing technology of laterite nickel ore can be divided into pyrometallurgical process and wet process. Among them, the wet process includes high-pressure acid leaching and reduction roasting-ammonia leaching, as well as processes such as atmospheric pressure acid leaching and heap leaching that have emerged in recent years. The process conditions of high-pressure acid leaching of laterite nickel ore are 255-260℃ and 5-6Mpa. It is necessary to add sulfuric acid. Generally, the acid-ore ratio is about 0.3 (concentrated sulfuric acid dosage: 1 ton of dry ore). The pressure and temperature of the entire leaching process are high, and the steam energy consumption and equipment performance parameters have high requirements. If the temperature and pressure of high-pressure acid leaching of laterite nickel ore can be reduced, the cost can also be reduced and the loss of equipment can be slowed down.
低冰镍作为红土镍矿火法冶炼的总结品，主要以镍铁合金相为主。红土镍矿与碳粉混合经过回转窑加热焙烧，使原矿中金属氧化物转变成金属单质，形成中间品镍铁合金(低冰镍)。一般产线上会进一步电炉加热，1500℃左右去除杂质，从而形式高冰镍，在此过程中消耗大量能耗，且造成Ni和Co的大量损失。如果能以低冰镍为原料进行处理，能避免镍钴的损耗，且降低能耗。As the final product of the pyrometallurgical smelting of laterite nickel ore, low-grade nickel matte is mainly composed of nickel-iron alloy phase. The laterite nickel ore is mixed with carbon powder and heated and roasted in a rotary kiln to convert the metal oxides in the original ore into metal elements, forming an intermediate nickel-iron alloy (low-grade nickel matte). Generally, the production line will be further heated in an electric furnace to remove impurities at around 1500°C, thereby forming high-grade nickel matte. A lot of energy is consumed in this process, and a large amount of Ni and Co are lost. If low-grade nickel matte can be used as raw material for processing, the loss of nickel and cobalt can be avoided and energy consumption can be reduced.
发明内容Summary of the invention
针对现有技术的不足，本发明的目的在于提供一种低冰镍混合红土镍矿的氧压浸出方法。In view of the deficiencies in the prior art, an object of the present invention is to provide an oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore.
本发明的目的通过以下技术方案实现：The purpose of the present invention is achieved through the following technical solutions:
一种低冰镍混合红土镍矿的氧压浸出方法，包括如下步骤：An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
(1)首先，对红土镍矿原矿进行选矿预处理，得到红土镍矿矿浆；然后将经过预处理的低冰镍和红土镍矿矿浆按照2：1～6的质量比混合，加入硫酸溶液进行氧压浸出反应，控制反应温度为180～220℃、压力为2.5～3.5Mpa，氧分压为20～30％；(1) First, the raw laterite nickel ore is pretreated to obtain laterite nickel ore pulp; then the pretreated low nickel matte and laterite nickel ore pulp are mixed in a mass ratio of 2:1-6, and sulfuric acid solution is added to carry out oxygen pressure leaching reaction, and the reaction temperature is controlled to be 180-220°C, the pressure is 2.5-3.5Mpa, and the oxygen partial pressure is 20-30%;
(2)氧压浸出反应结束后将产物过滤，调节滤液pH为3～5，生成沉淀， 过滤掉沉淀物后的液相经过萃取后，得到硫酸镍钴锰溶液。(2) After the oxygen pressure leaching reaction is completed, the product is filtered and the pH of the filtrate is adjusted to 3-5 to generate a precipitate. The liquid phase after filtering out the precipitate is extracted to obtain a nickel-cobalt-manganese sulfate solution.
优选的，步骤(1)所述红土镍矿原矿进行选矿预处理的方式为：红土镍矿原矿经过洗矿处理后经过筛分，-200目的矿浆进入成品罐，+200目大颗粒原矿一次经过螺旋溜槽和摇床处理，去除包含其中的铬铁矿，同时将尾矿至于球磨机中，钢球填充比50％的条件下，湿磨5min，再经过-200目筛，进入成品罐共同形成红土镍矿原矿浆，经过絮凝剂浓缩沉降后，得到矿浆浓度为28～37％的红土镍矿矿浆。Preferably, the laterite nickel ore in step (1) is pretreated for mineral processing in the following manner: the laterite nickel ore is washed and then sieved, the -200 mesh slurry enters the finished product tank, the +200 mesh large particle ore is processed by a spiral chute and a shaking table once to remove the chromite contained therein, and the tailings are placed in a ball mill, wet-milled for 5 minutes under the condition of a steel ball filling ratio of 50%, and then passed through a -200 mesh sieve and enter the finished product tank to form a laterite nickel ore slurry together, and after flocculant concentration and sedimentation, a laterite nickel ore slurry with a slurry concentration of 28-37% is obtained.
优选的，步骤(1)所述低冰镍的预处理方式为：低冰镍经过球磨机球磨2～4h，其中水含量为50％，低冰镍磨至50～200目。Preferably, the pretreatment method of the nickel matte in step (1) is: the nickel matte is ball milled for 2 to 4 hours, wherein the water content is 50%, and the nickel matte is ground to 50 to 200 mesh.
优选的，步骤(1)所述硫酸溶液的浓度为98wt％。Preferably, the concentration of the sulfuric acid solution in step (1) is 98 wt %.
优选的，步骤(1)所述硫酸溶液与经过预处理的低冰镍和红土镍矿矿浆总质量的比为0.1～0.3:1。Preferably, the ratio of the sulfuric acid solution in step (1) to the total mass of the pretreated low-matte nickel and laterite nickel ore slurry is 0.1 to 0.3:1.
优选的，步骤(1)所述氧压浸出反应的时间为3～8h。Preferably, the oxygen pressure leaching reaction time in step (1) is 3 to 8 hours.
优选的，步骤(2)所述过滤为压滤，压滤的渣相主要以Fe2O3为主，同时含有Al2O3、不溶于酸的硅酸盐，及Ni＜0.05％。Preferably, the filtration in step (2) is pressure filtration, and the slag phase of the pressure filtration is mainly composed of Fe 2 O 3 , and also contains Al 2 O 3 , acid-insoluble silicates, and Ni < 0.05%.
优选的，步骤(2)所述调节滤液pH的方式为：加入石灰石和石灰乳中的至少一种来调节pH。Preferably, the method of adjusting the pH of the filtrate in step (2) is to add at least one of limestone and lime milk to adjust the pH.
优选的，步骤(2)所述萃取的方式为：采用萃取剂Versatic10在pH＝2～3条件下，在溶液中选择性萃取Ni，以浓度为0.1～2mol/L的硫酸溶液进行反萃，制得高纯度硫酸镍溶液；再采用Cyanex272+PC-88A的二元萃取体系，在pH＝3～5条件下从水相溶液中协调萃取Co和Mn，最后采用浓度为0.01～0.5mol/L的硫酸溶液进行反萃，得到硫酸钴锰溶液。将其混合，即可制备得到高纯度硫酸镍钴锰溶液。Preferably, the extraction method in step (2) is: using the extractant Versatic10 to selectively extract Ni in the solution under the condition of pH=2-3, and back-extracting with a sulfuric acid solution with a concentration of 0.1-2 mol/L to obtain a high-purity nickel sulfate solution; then using a binary extraction system of Cyanex272+PC-88A to coordinately extract Co and Mn from the aqueous phase solution under the condition of pH=3-5, and finally back-extracting with a sulfuric acid solution with a concentration of 0.01-0.5 mol/L to obtain a cobalt manganese sulfate solution. By mixing them, a high-purity nickel cobalt manganese sulfate solution can be prepared.
本发明涉及的反应过程或机理为：The reaction process or mechanism involved in the present invention is:
由于低冰镍的主要成分为镍铁合金(Fe占45-60％，Ni占15-20％)，加入硫酸后，先与Fe反应，生产FeSO4，再在氧气氛围中氧化成Fe3+，再水解成Fe2O3进入渣相，同时释放硫酸，继续溶解低冰镍和红土镍矿中的金属氧化物。低冰镍中除了铁和镍外，还含有较多硫，在氧压条件下也能生成硫酸，能有效降低硫酸的额外加入量。铁单质与硫酸反应产生的H2与O2反应，以及硫转化成硫酸，均会释放大量的热量，维持整个高压釜体的温度，降低高压蒸汽的输入，降低处理成本。 Since the main component of nickel matte is nickel-iron alloy (Fe accounts for 45-60%, Ni accounts for 15-20%), after sulfuric acid is added, it first reacts with Fe to produce FeSO4 , then oxidizes to Fe3 + in an oxygen atmosphere, and then hydrolyzes to Fe2O3 and enters the slag phase, while releasing sulfuric acid to continue dissolving the metal oxides in nickel matte and laterite nickel ore. In addition to iron and nickel , nickel matte also contains a lot of sulfur, which can also generate sulfuric acid under oxygen pressure conditions, which can effectively reduce the additional amount of sulfuric acid added. The reaction of H2 produced by the reaction of iron element with sulfuric acid with O2 , as well as the conversion of sulfur into sulfuric acid, will release a large amount of heat, maintain the temperature of the entire autoclave body, reduce the input of high-pressure steam, and reduce processing costs.
与现有技术相比，本发明的有益效果包括：Compared with the prior art, the beneficial effects of the present invention include:
(1)本发明采用红土镍矿高压浸出相同的工艺产线，同时处理低冰镍和红土镍矿，降低高压釜的反应压力和反应温度，减少能耗。(1) The present invention adopts the same process production line for high-pressure leaching of laterite nickel ore to simultaneously process low-grade nickel matte and laterite nickel ore, thereby reducing the reaction pressure and reaction temperature of the autoclave and reducing energy consumption.
(2)硫酸用量降低，蒸汽用量降低，釜内反应涉及的放热反应能有效维持釜体温度。(2) The amount of sulfuric acid used is reduced, the amount of steam used is reduced, and the exothermic reaction involved in the reaction in the kettle can effectively maintain the kettle temperature.
(3)Fe2+在浸出体系中，能降低红土镍矿浸出液中Cr6+的存在，无需再加还原剂处理。(3) Fe 2+ in the leaching system can reduce the presence of Cr 6+ in the laterite nickel ore leaching solution without the need for adding reducing agents.
(4)红土镍矿火法工艺的中间产品低冰镍直接进入湿法工艺，避免镍钴的损失。(4) The intermediate product of the laterite nickel ore pyrometallurgical process, low-matte nickel, directly enters the wet process to avoid the loss of nickel and cobalt.
图1为本发明所述一种低冰镍混合红土镍矿的氧压浸出方法的流程图。FIG1 is a flow chart of an oxygen pressure leaching method for low-matte nickel mixed laterite nickel ore according to the present invention.
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
实施例和对比例所采用的低冰镍的组成为：Ni含量15～25％，Fe含量45～60％，Co含量0.1％，S含量8～15％。The composition of the low-matte nickel used in the embodiments and comparative examples is: Ni content 15-25%, Fe content 45-60%, Co content 0.1%, and S content 8-15%.
所述红土镍矿原矿的组成为：Ni含量1.1～1.3％，Co含量0.08～0.1％，Mn含量1～3％，Fe含量38～44％，Al含量2～3％，Mg含量2％左右。The composition of the laterite nickel ore is as follows: Ni content is 1.1-1.3%, Co content is 0.08-0.1%, Mn content is 1-3%, Fe content is 38-44%, Al content is 2-3%, and Mg content is about 2%.
所述硫酸溶液的浓度为98wt％。The concentration of the sulfuric acid solution is 98 wt %.
所述红土镍矿原矿进行选矿预处理的方式为：The method for the beneficiation pretreatment of the laterite nickel ore is as follows:
红土镍矿原矿经过洗矿处理后经过筛分，-200目的矿浆进入成品罐，+200目大颗粒原矿一次经过螺旋溜槽和摇床处理，去除包含其中的铬铁矿，同时将尾矿至于球磨机中，钢球填充比50％的条件下，湿磨5min，再经过-200目筛，进入成品罐共同形成红土镍矿原矿浆，经过絮凝剂浓缩沉降后，得到矿浆浓度为28～37％的红土镍矿矿浆。The laterite nickel ore is washed and sieved, and the -200 mesh slurry enters the finished product tank. The +200 mesh large-particle ore is processed by a spiral chute and a shaking table to remove the chromite contained therein. At the same time, the tailings are placed in a ball mill, wet-milled for 5 minutes under the condition of a steel ball filling ratio of 50%, and then passed through a -200 mesh sieve and enter the finished product tank to form a laterite nickel ore slurry. After flocculant concentration and sedimentation, a laterite nickel ore slurry with a slurry concentration of 28-37% is obtained.
所述低冰镍的预处理方式为：将低冰镍研磨至200目。The pretreatment method of the low-matte nickel is: grinding the low-matte nickel to 200 meshes.
实施例1Example 1
一种低冰镍混合红土镍矿的氧压浸出方法，包括如下步骤： An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
(1)首先，对红土镍矿原矿进行选矿预处理，得到红土镍矿矿浆；然后200g将经过预处理的低冰镍和400g红土镍矿矿浆按照1：2的质量比混合，加入60g硫酸溶液进行氧压浸出反应，所述硫酸溶液与经过预处理的低冰镍和红土镍矿矿浆总质量的比为0.1:1(即酸矿比为0.1)。(1) First, the raw laterite nickel ore is pretreated to obtain laterite nickel ore pulp; then 200 g of the pretreated low-grade nickel matte and 400 g of the laterite nickel ore pulp are mixed in a mass ratio of 1:2, and 60 g of sulfuric acid solution is added to carry out oxygen pressure leaching reaction, wherein the ratio of the sulfuric acid solution to the total mass of the pretreated low-grade nickel matte and the laterite nickel ore pulp is 0.1:1 (i.e., the acid-ore ratio is 0.1).
控制反应温度为220℃、压力为3.5Mpa，氧分压为30％；The reaction temperature was controlled at 220°C, the pressure was 3.5 MPa, and the oxygen partial pressure was 30%;
(2)氧压反应4h后将产物压滤，通过加入石灰石调节滤液pH为4.5，生成沉淀物，过滤掉沉淀物后的液相经过萃取后，得到硫酸镍钴锰溶液。(2) After 4 hours of oxygen pressure reaction, the product was filtered, and the pH of the filtrate was adjusted to 4.5 by adding limestone to generate a precipitate. The liquid phase after filtering out the precipitate was extracted to obtain a nickel-cobalt-manganese sulfate solution.
经过氧压浸出后，浸出液中pH在0.1～0.9之间，溶液中Ni浓度>20g/L，Co>0.5g/L，Fe<2g/L，Al<1.5g/L；渣相中Ni含量<0.08％。整个过程酸矿比降低至0.1，显著减少硫酸用量。After oxygen pressure leaching, the pH of the leaching solution is between 0.1 and 0.9, the Ni concentration in the solution is >20g/L, Co>0.5g/L, Fe<2g/L, Al<1.5g/L; the Ni content in the slag phase is <0.08%. The acid-ore ratio is reduced to 0.1 during the whole process, which significantly reduces the amount of sulfuric acid used.
实施例2Example 2
一种低冰镍混合红土镍矿的氧压浸出方法，包括如下步骤：An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
该实施例与实施例1的区别仅仅在于：The difference between this embodiment and embodiment 1 is only that:
步骤1中的低冰镍与红土镍矿矿浆比例为1:3，即200g将经过预处理的低冰镍和600g红土镍矿矿浆，其他条件与实施例1相同。The ratio of low-matte nickel to laterite nickel ore slurry in step 1 is 1:3, that is, 200g of pretreated low-matte nickel and 600g of laterite nickel ore slurry, and other conditions are the same as in Example 1.
改变低冰镍和红土镍矿比例后，浸出液中pH升至1.1，浸出液中Ni的含量>17g/L，Co>0.4g/L，Fe<2g/L，Al<1.5g/L；渣相中Ni含量<1.2％。低冰镍含量降低，会导致0.1的酸矿比不够，无法将Ni全部溶出，因此需要提高酸矿比，才能增加Ni和Co的浸出率。After changing the ratio of low-grade nickel matte and laterite nickel ore, the pH in the leaching solution rises to 1.1, the content of Ni in the leaching solution is >17g/L, Co>0.4g/L, Fe<2g/L, Al<1.5g/L; the content of Ni in the slag phase is <1.2%. The reduction of low-grade nickel matte content will result in an acid-ore ratio of 0.1 being insufficient to dissolve all Ni, so the acid-ore ratio needs to be increased to increase the leaching rate of Ni and Co.
实施例3Example 3
一种低冰镍混合红土镍矿的氧压浸出方法，包括如下步骤：An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
该实施例与实施例1的区别仅仅在于：The difference between this embodiment and embodiment 1 is only that:
氧分压降低至20％，其他条件不变。The oxygen partial pressure was reduced to 20%, and other conditions remained unchanged.
氧气在高压釜中的作用是氧化亚铁，同时与低冰镍中S和反应产生的H2结合，释放热量。氧分压降至20％时。浸出液中Fe的含量增加<4.2g/L，Ni和Co的含量均降低，Ni<15g/L，Co<0.35g/L；渣相中Ni和Co残留量也增加。这主要是由于O2含量降低，导致Fe2+无法完全被氧化，酸量降低，无法全部溶出Ni和Co。The role of oxygen in the autoclave is to oxidize ferrous iron, and at the same time combine with sulfur in the low nickel matte and the H2 produced by the reaction to release heat. When the oxygen partial pressure drops to 20%, the Fe content in the leaching solution increases by <4.2g/L, and the Ni and Co contents both decrease, Ni<15g/L, Co<0.35g/L; the residual Ni and Co in the slag phase also increases. This is mainly due to the decrease in O2 content, which leads to the inability of Fe2 + to be completely oxidized, the reduction in acidity, and the inability to completely dissolve Ni and Co.
实施例4Example 4
一种低冰镍混合红土镍矿的氧压浸出方法，包括如下步骤：An oxygen pressure leaching method for low-nickel matte mixed laterite nickel ore comprises the following steps:
该实施例与实施例1的区别仅仅在于： The difference between this embodiment and embodiment 1 is only that:
氧压反应的反应时间为2h，其他条件不变。The reaction time of the oxygen pressure reaction was 2 h, and other conditions remained unchanged.
缩短氧压反应时间。浸出液中Fe含量>15g/L，Ni<10g/L，Co<0.2g/L，Al<4g/L。反应时间不足，导致Fe3+还未转化完成，浸出率下降。Shorten the oxygen pressure reaction time. The Fe content in the leaching solution is >15g/L, Ni <10g/L, Co <0.2g/L, and Al <4g/L. Insufficient reaction time results in the incomplete conversion of Fe 3+ and a decrease in the leaching rate.
对比例1Comparative Example 1
一种红土镍矿的氧压浸出方法，步骤如下：An oxygen pressure leaching method for laterite nickel ore, the steps are as follows:
该对比例与实施例1的区别仅仅在于：步骤(1)中，未加入低冰镍，对比在相同条件下红土镍矿的浸出效果。The only difference between this comparative example and Example 1 is that in step (1), no low-matte nickel is added, and the leaching effect of laterite nickel ore under the same conditions is compared.
未添加低冰镍的情况下，在此条件下进行高压浸出，红土镍矿中Ni和Co的浸出率基本均小于10％。较低的温度和压力，无法使促进反应进行，同时酸矿比较低，无法溶出Ni和Co。浸出液的最终pH＝3，Ni<1g/L，Co<0.02g/L，Fe<7g/L，Al<5g/L。Without adding low-grade nickel matte, high-pressure leaching was performed under this condition, and the leaching rates of Ni and Co in laterite nickel ore were basically less than 10%. The lower temperature and pressure could not promote the reaction, and the acid ore was relatively low, so Ni and Co could not be dissolved. The final pH of the leaching solution was 3, Ni<1g/L, Co<0.02g/L, Fe<7g/L, and Al<5g/L.
对比例2Comparative Example 2
一种硫酸镍钴锰溶液的制备方法，步骤如下：A method for preparing a nickel-cobalt-manganese sulfate solution, comprising the following steps:
该对比例与实施例1的区别仅仅在于：步骤(2)中浸出液不加入石灰石调节pH，除铁铝杂质，直接进行萃取，其他条件不变。The difference between this comparative example and Example 1 is that in step (2), no limestone is added to the leachate to adjust the pH and remove iron and aluminum impurities, and the extraction is carried out directly, while other conditions remain unchanged.
浸出液中Fe和Al的含量较高，对萃取剂Versatic10选择性萃取Ni有明显影响。降低了Ni的萃取率，从98％的萃取率降低至64％。进入负载有机相的Fe和Al影响萃取剂的重复利用性能。The high content of Fe and Al in the leachate has a significant impact on the selective extraction of Ni by the extractant Versatic 10. The Ni extraction rate is reduced from 98% to 64%. The Fe and Al entering the loaded organic phase affect the reuse performance of the extractant.
以上所述本发明的具体实施方式，并不构成对本发明保护范围的限定。任何根据本发明的技术构思所作出的各种其他相应的改变与变形，均应包含在本发明权利要求的保护范围内。 The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.
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