JP2015227510A - Wet refining method of nickel oxide ore - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wet refining method of nickel oxide ore based on high-temperature pressurized acid leaching which achieves a high iron oxidation rate because most of iron is immobilized in leach residue in the form of hematite, suppresses the use amount of sulfuric acid in leaching and leaches nickel and cobalt at high leach rates.SOLUTION: A wet refining method of nickel oxide ore includes a step of adding sulfuric acid to an ore slurry of nickel oxide ore, subjecting the slurry to a leach treatment by using high-pressure air and high-pressure water vapor to obtain a leachate containing nickel and cobalt. In the step of obtaining the leachate, the blowing ratio is adjusted so that the oxygen purity of a blowing gas consisting of high-pressure air and high-pressure oxygen is 21-60%; with the oxygen purity kept, the oxygen blowing amount is set to be 200-600 [Nm-O/t-C] per ton of carbon contained in the ore slurry and charged in the step; the oxidation-reduction potential (relative to Ag/AgCl) in the leach treatment is controlled to 400-650 mV.

Description

  The present invention relates to a method for hydrometallizing nickel oxide ore by leaching and recovering nickel and cobalt from nickel oxide ore using acid under high temperature and pressure.

  Conventionally, as a smelting process in which nickel and cobalt are separated from iron and recovered from nickel oxide ore containing nickel in an amount of 1 to 2% by weight, for example, nickel oxide ore is roasted and nickel content is recovered. Smelting and then smelting and then smelting to produce a mat containing nickel sulfide, or after reducing and roasting nickel oxide ore, There has been a reduction roasting-leaching method in which nickel and cobalt are leached.

  However, these smelting processes include a dry processing step for drying and roasting raw ores with high adhering moisture, and it is impossible to selectively reduce only nickel and cobalt. However, there was a problem that there was a lot of waste in terms of cost. Therefore, it has been desired to develop a process that can be carried out easily and at low cost for these smelting processes.

  In recent years, attention has been paid to a high pressure acid leaching method using sulfuric acid as a wet smelting method of nickel oxide ore. Unlike the conventional dry smelting method, which is a conventional nickel oxide ore smelting method, this method does not include dry processes such as reduction and drying processes, and is a consistent wet process. Is advantageous. Further, this method has an advantage that a sulfide containing nickel and cobalt whose nickel quality is increased to about 50% by weight (hereinafter also referred to as “nickel / cobalt mixed sulfide”) can be obtained. .

  This high-temperature pressure acid leaching method includes, for example, an ore slurry preparation step (corresponding to the “first step” below) in which a raw material nickel oxide ore is pulverized to a predetermined size to form a slurry, A leaching step (corresponding to the “second step” below) in which sulfuric acid is added and a leaching treatment is performed at a high temperature and high pressure of 200 ° C. or higher using an autoclave or the like, and a leaching residue in the leaching slurry; Solid-liquid separation process for separating the leachate containing nickel and cobalt, for adjusting the pH of the leachate containing impurity elements together with nickel and cobalt, and for recovering the purified nickel containing neutralized starch slurry containing impurity elements such as iron A neutralization step for producing a mother liquor, and a sulfidation step for producing a nickel / cobalt mixed sulfide and a poor liquor by supplying a sulfur recovery agent such as hydrogen sulfide gas to the nickel recovery mother liquor. For example, see Patent Document 1.).

By the way, in the high-temperature pressure acid leaching method, in the leaching process, iron as the main impurity is converted into hematite (Fe ₂ O ₃ ) by controlling the oxidation-reduction potential and temperature of the leaching solution in the pressure leaching reactor. Since it is fixed to the leaching residue and nickel and cobalt can be leached selectively with respect to iron, there is a great merit. On the other hand, nickel oxide ores with large variations in ore composition, organic components, etc. are directly leached without a roasting process. There was a problem that the oxidation-reduction potential (ORP) fluctuated greatly.

  For example, when the oxidation-reduction potential at the time of leaching is too high, chrome contained in nickel oxide ore is leached in a state of being oxidized to hexavalent. In order to remove this hexavalent chromium in the subsequent neutralization process or wastewater treatment process, it is necessary to reduce it to trivalent using a reducing agent, which inevitably increases the smelting cost. Become. If the reduction treatment is not performed, there is a problem that chromium or impurities are contained in nickel or cobalt products, or chromium remains in the final liquid of the waste water treatment. On the other hand, if the redox potential at the time of leaching is too low, titanium used in the autoclave as a corrosion-resistant material is deteriorated, and the high-temperature thermal hydrolysis reaction of iron is suppressed, so that a large amount of iron remains in the leachate. In this neutralization treatment step, there is a problem that the amount of chemical used and the amount of nickel and cobalt coprecipitation are increased, that is, the loss is increased.

  As a solution to this, for example, there is a method in which one or more of sulfur and carbon compounds are added to the ore slurry, and the leaching is performed by controlling the redox potential (Ag / AgCl standard) of the leaching solution to 400 to 600 mV. (For example, refer to Patent Document 2). In this method, the added sulfur and carbon compound are allowed to act as a reducing agent, thereby reducing the redox potential and controlling it to 600 mV or less at which hexavalent chromium is not eluted. If the oxidation-reduction potential is less than 400 mV, not only the oxidation hydrolysis reaction of iron becomes poor, but also the corrosion resistance of the equipment material is impaired. Therefore, the addition amount of sulfur or carbon compound is adjusted to adjust the oxidation-reduction potential to 400-600 mV. To control.

  Moreover, the target oxidation-reduction potential (Ag / AgCl reference | standard) is controlled to 400-600 mV by changing these compounding ratios of the ore seed | species from which sulfur and carbon compound content differ, without adding a reducing agent. A method is also disclosed (for example, see Patent Document 3).

  In the leaching process in the leaching process using the method described in Patent Document 2 above, the leached iron is oxidized to hematite and hydrolyzed, so normally high-pressure air is used as the oxidizing agent and the inside of the reaction vessel is added. It is essential to keep it under pressure. However, this method does not disclose the use conditions of high-pressure air. This method deals with fluctuations in redox potential due to variations in ore composition and organic component content, and in particular, prevents the reduction of “iron oxidation rate” and the elution of chromium to trivalent iron due to the reduction in redox potential. From the viewpoint of reducing the oxidation-reduction potential by causing the added sulfur and carbon compounds to act as a reducing agent, an excessive amount of high-pressure air was blown in order to control the oxidation-reduction potential. As a result, the amount of exhaust gas from the pressurized reaction vessel increases, the heat loss associated with it increases, and the amount of high-pressure steam used for temperature adjustment increases to compensate for it and maintain the temperature in the pressurized reaction vessel. As a result, the energy cost was worsened.

  Moreover, in the leaching process in the leaching step using the method described in Patent Document 3, in the first step of preparing the ore slurry, mainly by changing the mixing ratio of ore species having different sulfur and carbon compound contents, The carbon quality of the solid content in the target ore slurry is adjusted in advance to suppress excessive high-pressure air blowing during the leaching process in the second step. However, depending on the ore species, their composition and organic component content vary, so that not only is the composition ratio limited, but depending on the mixing ratio, the solid magnesium and aluminum grades in the ore slurry can be increased. Invite. These impurities such as magnesium and aluminum react with sulfuric acid added in the acid leaching in the second step and consume the sulfuric acid, so that the leaching rate of nickel and cobalt is lowered. In order to avoid this, it is necessary to add an excessive amount of sulfuric acid, but in that case, it leads to an increase in the amount of chemicals used in the subsequent neutralization treatment step and an increase in the amount of coprecipitation of nickel and cobalt. There was a problem.

JP-A-2005-350766 JP 2005-281733 A JP 2009-197298 A

  The present invention has been proposed in view of such circumstances, and in a hydrometallurgical method using high-temperature pressure acid leaching of nickel oxide ore, most of iron as a main impurity is leached in the form of hematite. To achieve a high iron oxidation rate for immobilization on the surface, reduce the use of sulfuric acid during leaching, reduce chemical costs, and provide a method that can leach nickel and cobalt at a high leaching rate It is in.

  The inventors of the present invention have made extensive studies to achieve the above-described object. As a result, depending on the amount of carbon contained in the ore slurry and obtaining the leachate, part of the high-pressure air used to maintain the oxidizing atmosphere is replaced with high-pressure oxygen to increase the oxygen purity and the oxygen injection amount Is maintained within a predetermined range, it is possible to control the ORP of the liquid at the time of leaching to an optimum range, and it is possible to reduce the amount of sulfuric acid used by suppressing the quality of magnesium and aluminum as impurities during acid leaching. The present invention was completed.

That is, the method for hydrometallurgy of nickel oxide ore according to the present invention is a step of adding sulfuric acid to an ore slurry of nickel oxide ore and performing a leaching treatment using high-pressure air and high-pressure steam to obtain a leachate containing nickel and cobalt. In the step of obtaining the leachate, adjusting the blowing ratio so that the oxygen purity of the blowing gas composed of high-pressure air and high-pressure oxygen is 21 to 60%, and And leaching with an oxygen blowing amount of 200 to 600 [Nm ³ —O ₂ / tC] per ton of carbon contained in the ore slurry and charged in the process while maintaining the oxygen purity The oxidation-reduction potential (Ag / AgCl reference) in the treatment is controlled to 400 to 650 mV.

  Moreover, in the hydrometallurgy method of nickel oxide ore according to the present invention, the ore slurry is prepared such that the slurry concentration is 25 to 45% by weight.

  Moreover, in the hydrometallurgy method of the nickel oxide ore according to the present invention, the pH of the leachate obtained in the step of obtaining the leachate is 0.1 to 1.0.

  In the method for hydrometallizing nickel oxide ore according to the present invention, the high-pressure air and the high-pressure oxygen are mixed in advance so as to have the oxygen purity.

  In the method for hydrometallizing nickel oxide ore according to the present invention, carbon dioxide gas generated in the step of obtaining the leachate is released by an automatic pressure control system.

  According to the hydrometallurgy method of nickel oxide ore according to the present invention, most of iron as an impurity can be oxidized at a high oxidation rate and fixed as a leaching residue in the form of hematite. In addition, it is possible to increase the processing amount of ore with high carbon quality, which was difficult due to inhibition of iron oxidation in the past, so that the quality of magnesium and aluminum can be kept low, and the amount of sulfuric acid used can be suppressed. Nickel and cobalt can be leached at a high leaching rate.

It is a graph showing the relationship between the oxygen blowing amount per ton of unit carbon contained in the treated ore slurry in Example 1 and the oxidation-reduction potential (ORP) of the acid leaching solution. It is a graph showing the relationship between the carbon quality of the ore in Example 1, and the oxidation-reduction potential (ORP) of an acid leaching solution. It is a graph showing the relationship between the carbon quality of the ore and the (Fe (III) / Fe, total) ratio representing the iron oxidation rate in Example 1. The graph showing the relationship between the oxygen partial pressure in the pressurization reaction container in Example 1 and the oxidation reduction potential (ORP) of an acid leaching solution is shown.

  Hereinafter, a specific embodiment (hereinafter referred to as “the present embodiment”) of a method for hydrometallizing nickel oxide ore according to the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and various modifications can be made without departing from the gist of the present invention.

  The nickel oxide ore wet smelting method according to the present embodiment (hereinafter, also simply referred to as “wet smelting method”) includes a first step of slurrying nickel oxide ore to prepare an ore slurry, and the prepared ore. And a second step of adding a sulfuric acid to the slurry and performing a leaching treatment using high-pressure air and high-pressure steam to obtain a leachate containing nickel and cobalt.

In this hydrometallurgical method, first, the amount of carbon contained in the ore slurry produced in the first step and charged in the second step is measured. The amount of carbon can be measured by measuring the carbon quality and flow rate in the ore slurry. And in a 2nd process, while adjusting the blowing ratio so that the oxygen purity of the blowing gas which consists of high pressure air and high pressure oxygen may become 21 to 60%, the amount of carbon contained in the ore slurry is the oxygen blowing amount The oxidation-reduction potential (Ag / AgCl standard) in the leaching process is controlled to 400 to 650 mV as 200 to 600 [Nm ³ —O ₂ / tC] per ton.

  Thus, in the hydrometallurgical method according to the present embodiment, in the leaching process of the second step, the blowing gas composed of high-pressure air and high-pressure oxygen is matched to the amount of carbon (weight) charged into the step. It is important to adjust the oxygen purity and to adjust the oxygen blowing amount of the blowing gas adjusted to a predetermined oxygen purity.

  The amount of carbon can be calculated by measuring the carbon quality and the flow rate by a known method in the ore slurry being transferred from the first step to the second step. For example, the carbon quality can be calculated by a general carbon sulfur analyzer that performs high-frequency combustion in an oxygen stream and measures it by an infrared absorption method. The flow rate can be calculated from the measured values of the density meter and the electromagnetic flow meter.

This makes it possible to adjust the partial pressure of oxygen in the pressurized reaction vessel (leaching vessel) that performs the leaching process in accordance with the amount of carbon in the ore slurry, and the oxidation-reduction potential (Ag / AgCl standard) of the leaching solution is 400. It can be controlled to ˜650 mV. As a result, most of iron as a main impurity can be oxidized at a high oxidation rate (high iron oxidation rate) and fixed as a leaching residue in the form of hematite (Fe ₂ O ₃ ). The amount used can be suppressed and nickel and cobalt can be leached at a high leaching rate.

(First step)
First, in the first step, as described above, nickel oxide ore is slurried to prepare an ore slurry.

  As the raw material nickel oxide ore, so-called laterite ores such as limonite ore and saprolite ore are mainly used. The nickel content in the laterite ore is usually 0.5 to 3.0% by weight, and is contained as a hydroxide or a siliceous clay (magnesium silicate) mineral. The iron content is 10 to 50% by weight and is mainly in the form of trivalent hydroxide (goethite, FeOOH), but partly divalent iron is contained in the siliceous clay. .

  In the first step, the nickel oxide ore described above is crushed and ground in water to form a slurry. Thereafter, for example, excess water in the slurry is removed and concentrated using a solid-liquid separation device such as thickener to prepare an ore slurry having a predetermined concentration. At this time, in the first step, the carbon quality in the solid content of the ore slurry may be adjusted to be within a predetermined range by the mixing ratio of plural kinds of nickel oxide ores having different carbon amounts as raw materials.

  Here, in the conventional hydrometallurgical method using high-temperature pressure acid leaching, there are those that contain a relatively large amount of organic components depending on the ore type of the mined nickel oxide ore, and the mixing ratio is high. In this case, the oxidation-reduction potential during leaching was significantly reduced. When the oxidation-reduction potential is lowered in this way, the oxidation reaction of iron in the ore is not promoted. As a result, a large amount of divalent iron ions remain in the leachate. It was difficult to separate iron from the mixed aqueous solution), or the operating material cost required for the separation was increased. In addition, the corrosion resistance of the pressurized reaction vessel and the incidental equipment is also deteriorated.

  Therefore, it is important to maintain the oxidation-reduction potential in the optimum range in the leaching process in the second step described later. Specifically, the redox potential (Ag / AgCl standard) of the solution during leaching is preferably controlled to 400 to 650 mV, and more preferably 500 to 600 mV. That is, if the oxidation-reduction potential at the time of leaching is less than 400 mV, not only the oxidation reaction of iron becomes poor, but also the corrosion resistance of the equipment material is impaired. On the other hand, when the oxidation-reduction potential exceeds 650 mV, iron in the acid leachate is oxidized from divalent to almost completely trivalent, and at the same time, chromium is oxidized to hexavalent, and chromium is added to nickel and cobalt products. There is a problem that chromium is contained as impurities or remains in the final liquid of the waste water treatment.

  Therefore, first, in order to grasp the amount of carbon per unit time (ton / hour) charged in the second step described later, the carbon quality (% by weight) contained in the produced ore slurry is measured and combined. The flow rate per unit time (ton / hour) charged in the second step is measured. The amount of carbon (A) per unit time is calculated and grasped from the measured values of the carbon quality and the flow rate per unit time.

  The carbon quality (% by weight) contained in the ore slurry is not particularly limited, but in order to stabilize the amount of carbon per unit time, the carbon quality in the solid content of the ore slurry is 0.1 to 0.00. It is preferable to adjust to 5 wt%, more preferably 0.15 to 0.20 wt%.

  As a method for adjusting the carbon quality in the solid content in the ore slurry, for example, the carbon quality in the nickel oxide ore to be treated is periodically analyzed, and the mixing ratio is determined based on the analysis result. There is a method of blending.

  If the carbon grade in the solid content of the ore slurry fluctuates, especially when it fluctuates in a wider range than the above range, the fluctuation of the carbon amount per unit time increases, and in the second step, the range of adjustment of the oxygen concentration and flow rate to be blown is large. Therefore, it is disadvantageous in terms of equipment capacity and life.

  The slurry concentration of the ore slurry prepared in the first step is not particularly limited because it largely depends on the nature of the nickel oxide ore to be treated, but the slurry concentration of the leaching slurry is preferably higher, usually Approximately 25 to 45% by weight. That is, if the slurry concentration is less than 25% by weight, a large facility is required to obtain the same residence time during leaching, and the amount of acid added also increases to adjust the residual acid concentration. Moreover, the nickel concentration of the obtained leachate becomes low. On the other hand, if the slurry concentration exceeds 45% by weight, the scale of the equipment can be reduced, but the viscosity of the slurry itself (yield stress) becomes high, and there is a problem that conveyance is difficult (occurrence of frequent blockage, energy is required, etc.). Will occur.

(Second step)
Next, in the second step, sulfuric acid is added to the ore slurry, high-pressure air as an oxidant and high-pressure steam as a heating source are blown in, and leaching is performed while stirring at a predetermined pressure and temperature. A leaching slurry comprising a leaching solution containing nickel and cobalt and a leaching residue is obtained.

  Specifically, the ore slurry is stirred by pressurizing to about 3 to 6 MPaG under a high temperature condition of about 220 to 280 ° C. to form a leaching slurry. Therefore, in this leaching process, a high-temperature pressurized container (pressurized reaction container) (autoclave) is used so as to be able to cope with these processing conditions.

  In this second step, as a sulfate such as nickel or cobalt, by a leaching reaction represented by the following formulas (1) to (3) and a high temperature hydrolysis reaction represented by the following formulas (4) and (5): And the immobilization of the leached iron sulfate as hematite is performed. However, since immobilization of iron ions does not proceed completely, the leaching slurry obtained usually contains divalent and trivalent iron ions in addition to nickel and cobalt.

"Leaching reaction"
MO + H ₂ SO ₄ ⇒ MSO ₄ + H ₂ O (1)
(In the formula, M represents Ni, Co, Fe, Zn, Cu, Mg, Cr, Mn, etc.)
2FeOOH + 3H ₂ SO ₄ ⇒ Fe ₂ (SO ₄ ) ₃ + 4H ₂ O (2)
FeO + H ₂ SO ₄ ⇒ FeSO ₄ + H ₂ O (3)

"High temperature hydrolysis reaction"
2FeSO ₄ + H ₂ SO ₄ + 1 / 2O ₂
⇒ Fe ₂ (SO ₄ ) ₃ + H ₂ O (4)
Fe ₂ (SO ₄ ) ₃ + 3H ₂ O => Fe ₂ O ₃ + 3H ₂ SO ₄ (5)

  Although it does not specifically limit as temperature in this leaching process, As mentioned above, 220-280 degreeC is preferable and 240-270 degreeC is more preferable. By carrying out the reaction in such a temperature range, iron can be immobilized as hematite. If the temperature is less than 220 ° C., the rate of the high-temperature thermal hydrolysis reaction is slow, so that iron remains dissolved in the reaction solution, increasing the load in the neutralization step of the subsequent step for removing iron and separation from nickel. Becomes very difficult. On the other hand, when the temperature exceeds 280 ° C., the high-temperature thermal hydrolysis reaction itself is promoted, but it is not only difficult to select the material of the container used for the high-temperature pressure leaching, but also the cost of high-pressure steam for increasing the temperature increases. Inappropriate.

The amount of sulfuric acid to be added is not particularly limited, but is preferably about 200 to 250 [kg-H ₂ SO ₄ / t-dry Solid] per ton of dry ore, for example. If the amount of sulfuric acid added per ton of dry ore is too large, the cost associated with the use of sulfuric acid increases, and the amount of neutralizing agent used in the neutralization step in the subsequent step increases.

  In addition, it is preferable that the pH of the obtained leaching liquid is adjusted to 0.1-1.0 from the viewpoint of the filterability of the leaching residue containing the hematite produced | generated in the solid-liquid separation process.

Here, in the conventional method, it was difficult to control the oxidation-reduction potential to 650 mV or less without blowing excessive high-pressure air. Specifically, it was necessary to set an air blowing amount of 700 to 800 Nm ³ per carbon unit weight (1 ton) in the solid-liquid content of the ore slurry.

  Moreover, if it is going to change the mixing | blending of several types of nickel oxide ore in order to make the carbon quality relevant to a carbon unit weight as small as possible, content of impurities, such as magnesium and aluminum, will rise in solid content. Then, in the leaching reaction, sulfuric acid is consumed by these impurities, and it is necessary to add an excessive amount of sulfuric acid to make up for it, and the leaching rate of nickel and cobalt to be leached with respect to the added sulfuric acid amount is remarkably lowered. In addition, an excessive amount of high-pressure air needs to be blown in order to maintain the oxidizing atmosphere during the leaching reaction.

  Therefore, in the hydrometallurgical method according to the present embodiment, the blown oxygen purity is adjusted to a predetermined value according to the amount of carbon per unit time (ton / hour) charged in the second step. Specifically, high-pressure oxygen is used together with high-pressure air, and the blowing ratio is adjusted so that the oxygen purity (concentration) is 21 to 60%. Thereby, the oxygen partial pressure in a pressurization reaction container can be adjusted to 100-400kPaG, the influence of the oxidation reaction with respect to iron can be controlled, and an excessive fluctuation | variation can be suppressed.

  When the oxygen purity is less than 21%, it becomes almost the same as when only high-pressure air is blown, and it becomes necessary to blow in an excessive amount of high-pressure air, and the carbon quality of the ore to be blended in the ore slurry is as low as possible. It becomes necessary to suppress, and the quality of impurities such as magnesium and aluminum is increased. On the other hand, when the oxygen purity exceeds 60%, an excessively oxidizing atmosphere is formed, so that it becomes difficult to control the oxidation-reduction potential within the range of 400 to 650 mV, and the chromium in the ore is oxidized to deteriorate the product quality. .

The adjustment of the injection ratio of high-pressure air and high-pressure oxygen depends on the carbon amount per unit time (ton / hour) charged in the second step, which is obtained from the above-described carbon quality and flow rate per unit time. The supply rate (ratio) of high-pressure air and high-pressure oxygen is adjusted so that the oxygen blowing amount is 200 to 600 [Nm ³ —O ₂ / tC] per carbon amount.

  Specifically, when the amount of carbon per unit time increases, the ratio of high-pressure oxygen is increased within the above-described oxygen purity range, and the increase in the total amount of gas blown into the second step is suppressed, and the amount of exhaust gas The increase in heat loss accompanying the increase, and hence the deterioration of the energy cost accompanying the increase in the amount of high-pressure steam used in the second step is avoided.

  Further, the high-pressure air and high-pressure oxygen are blown into the pressurized reaction vessel after mixing (preliminary mixing) in advance, for example, in a mixing tube or the like so as to achieve the above-described blowing ratio of oxygen purity. It is preferable to blow. Here, high-pressure oxygen is supplied into the leaching vessel from an oxygen production plant or the like via, for example, a titanium (Ti) pipe. Titanium (Ti) is a material that is also preferably used for an autoclave inner paste or the like in order to industrially implement this wet smelting method. The pipe is provided with a check valve such as a check valve, but the cutting waste cut by the check valve may cut a part of the oxide film (TiO) formed on the Ti pipe. When the oxide film formed on the Ti pipe is scraped in this way, high-pressure oxygen having a concentration of, for example, 90% or more supplied to the shaved portion is in direct contact, and oxygen and titanium react rapidly. The piping may be damaged. At this time, the high-pressure oxygen to be blown in is mixed with high-pressure air in a predetermined ratio and then supplied through the pipe, so that high-concentration oxygen can be prevented from coming into contact with the pipe, resulting in damage to the pipe. Can be prevented. Further, from the viewpoint of preventing such damage to the piping, the oxygen purity may be preliminarily mixed so as to be 21 to 60% as described above, but preliminarily mixed with the upper limit of about 30%. It is more preferable.

  As the high-pressure air and high-pressure oxygen to be blown in, high-pressure gas usually used for industrial use can be used, for example, one having a pressure of 3 to 6 MPaG can be used. In addition, also about the high pressure steam, the high pressure steam normally used for industry can be used, for example, the thing of the pressure of 3-6 MPaG can be used.

  The oxygen partial pressure in the pressurized reaction vessel is adjusted by adjusting the blowing ratio of high-pressure air and high-pressure oxygen as described above in order to control the redox potential of the leachate to a predetermined value. It is performed by setting it to a predetermined range. In normal operation, carbon dioxide gas generated at the time of leaching is purged as it is in the pressurized reaction vessel, and an oxidizing atmosphere can be maintained. Therefore, it is preferable that the generated carbon dioxide gas is released in a timely manner along with the generated exhaust gas by an automatic pressure control system provided in the pressurized reaction vessel. Thereby, the oxygen partial pressure in the pressurized reaction vessel can be appropriately adjusted to a range of 100 to 400 kPaG, and an excessive oxidizing atmosphere can be prevented.

  Further, in the hydrometallurgical method according to the present embodiment, according to the ore slurry processing amount, while maintaining the above-described oxygen purity by keeping the mixing ratio of high-pressure air and high-pressure oxygen constant, By changing, it adjusts so that it may become predetermined | prescribed oxygen blowing amount.

Specifically, the oxygen blowing amount is adjusted to 200 to 600 [Nm ³ —O ₂ / tC] per ton of carbon contained in the ore slurry. As a result, even in continuous leaching reactions, the oxidizing atmosphere in the pressurized reaction vessel is stably controlled to a predetermined value, so that the redox potential of the leaching solution can be efficiently controlled within the range of 400 to 650 mV. it can. As a result, the iron oxidation rate (Fe (III) / Fe, Total × 100) representing the ratio of the trivalent iron ion concentration to the total iron ion concentration in the leachate becomes 90% or more, particularly in the ore slurry described above. If the carbon content of the solid content is 0.15% by weight or less, it becomes approximately 100%, and iron in the ore can be effectively fixed as a leaching residue in the form of hematite.

Regarding the oxygen blowing amount described above, when the oxygen blowing amount is less than 200 [Nm ³ —O ₂ / tC], the redox potential of the leachate is lowered, and it becomes difficult to control the redox potential to 400 mV or higher. Thereby, not only the oxidative hydrolysis reaction of iron becomes poor, but also the corrosion resistance of the equipment material may be impaired. On the other hand, when the oxygen blowing amount exceeds ^{600 [Nm 3 -O 2 / t} -C], although the redox potential of the leaching solution is increased, the heat loss is increased with increasing amount of exhaust gas, the temperature is maintained Therefore, the amount of high-pressure steam used is increased.

As described above, in the hydrometallurgical method according to the present embodiment, high-pressure oxygen is blown together with high-pressure air in order to maintain the oxidizing atmosphere, that is, a part of the blown high-pressure air is replaced with high-pressure oxygen and pressurized. The oxygen purity injected into the reaction vessel is increased to 21 to 60%, and the oxygen injection amount per unit time of carbon is 200 to 600 [Nm ³ —O ₂ / tC] while maintaining the oxygen purity. And Thereby, the oxidation reduction potential (Ag / AgCl reference | standard) of the solution at the time of leaching is controlled to the optimal range of 400-650 mV, and the high iron oxidation rate to trivalent iron can be achieved.

  Moreover, it becomes possible to raise the carbon quality in a processing ore by doing in this way. In other words, it is possible to increase the amount of ore having a high carbon quality, which has been difficult due to the inhibition of iron oxidation in the past, whereby the quality of magnesium and aluminum can be kept low. Therefore, in the leaching reaction, the consumption of sulfuric acid by these magnesium and aluminum impurities can be suppressed, the amount of sulfuric acid used can be suppressed, and the leaching inhibition of nickel and cobalt (coexistence to the leaching residue of nickel and cobalt can be reduced). Sinking) can be prevented. In addition, since the amount of sulfuric acid used is suppressed in this way, the amount of chemical (neutralizing agent) used for neutralization treatment can be reduced in the neutralization step of the subsequent step, and the cost of chemicals used in operation can be reduced. Can be reduced.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples of the present invention, but the present invention is not limited to these examples.

  In addition, the analysis of the metal used by the Example and the comparative example used ICP emission spectrometry. The carbon quality was measured by a general carbon sulfur analyzer that was subjected to high-frequency combustion in an oxygen stream and measured by an infrared absorption method, and the flow rate was calculated from the measured values of a density meter and an electromagnetic flow meter.

(Overview)
An overview of the examples and comparative examples is as follows. That is, a nickel oxide ore having a carbon (C) grade of solid content in the ore slurry of 0.3 wt% or less, a nickel grade of 1.15 to 1.35 wt%, and an iron grade of 40 to 46 wt%, A slurry having a solid content of about 40 to 45% by weight was put into a pressurized reaction vessel and continuously leached.

  At that time, sulfuric acid was added so that the concentration of free sulfuric acid in the reaction final solution was about 50 g / l, and at the same time, high-pressure steam of about 5 MPaG was blown in and kept at a temperature of 245 ° C. with stirring, and the obtained leaching The iron concentration and redox potential (ORP) (Ag / AgCl electrode standard) of the slurry were measured.

In the examples, about 5 MPaG of high-pressure air and high-pressure oxygen were blown into the pressurized reaction vessel while adjusting the oxygen purity within the range of 21 to 60%. On the other hand, in the comparative example, high-pressure oxygen was not blown but only high-pressure air was blown, and thus the oxygen purity was 20%. In Examples, can be blown with an oxygen blowing amount of carbon content (A) 1 tonne _{^{200~600 [Nm 3 -O 2 / t}} -C], as a result, the oxygen partial pressure in the vessel It became 100-350 kPaG.

On the other hand, in Comparative Example 2, since the carbon load is high, only 167 [Nm ³ —O ₂ / tC] of oxygen can be injected per ton of carbon in the solid content of the ore slurry. The oxygen partial pressure in the container was about 90 kPaG.

In addition, the amount of sulfuric acid used was 200 to 235 [kg-H ₂ SO ₄ / t-dry Solid] per ton of dry ore in the examples, while 240 kg in the comparative example. −H ₂ SO ₄ / t-dry Solid] or more.

  Further, a calcium carbonate slurry was added to the obtained leaching slurry, and trivalent Fe ions were neutralized and removed by oxidation to analyze the concentration of divalent Fe remaining in the liquid. Based on the analysis result of the divalent Fe concentration, the leachate was obtained using the total Fe concentration of the leachate in the leach slurry, the divalent Fe concentration in the neutralized solution and the trivalent Fe concentration of the leachate calculated backward from the liquid amount. The iron oxidation rate ((trivalent iron concentration / total iron concentration) × 100) was determined.

FIG. 1 shows the amount of oxygen blown per ton of unit carbon contained in the treated ore slurry and the redox potential of the acid leaching solution in the pressurized reaction vessel (autoclave). Regardless of (or not limited to) the carbon quality of the ore, the oxygen blowing amount per ton of unit carbon contained in the treated ore slurry is in the range of 200 to 600 [Nm ³ —O ₂ / tC]. It can be seen that the oxidation-reduction potential of the acid leaching solution is 500 to 650 mV.

  On the other hand, the relationship between the carbon grade of the ore and the ORP of the acid leaching solution is as follows. 2 and 3 show the measurement results. FIG. 2 is a graph showing the relationship between the ore carbon quality and the acid leaching solution ORP, and FIG. 3 shows the ore carbon quality and the iron oxidation rate (Fe (III) / Fe, total) ratio. It is a graph showing a relationship.

  As shown in the graphs of FIGS. 2 and 3, if the ore has a carbon grade of 0.15 to 0.30% by weight, the oxidation-reduction potential of the leachate is 500 to 650 mV, as well as iron in the leachate. It can be seen that the oxidation rate is 90% or more. Moreover, if the carbon grade of an ore is 0.15 weight% or less, it turns out that the iron oxidation rate in a leaching solution will be 100%.

  FIG. 4 is a graph showing the relationship between the partial pressure of oxygen in the pressurized reaction vessel and the ORP of the acid leaching solution. As shown in the graph of FIG. 4, the oxygen purity of the gas blown into the container is increased, and the oxygen partial pressure in the pressurized reaction container is increased by increasing the oxygen blowing amount, thereby It can be seen that the ORP rises proportionally. In addition, since this ORP is affected by the carbon quality in the solid content of the ore slurry charged into the reaction vessel, it is necessary to adjust the oxygen partial pressure in the pressurized reaction vessel in order to maintain a constant ORP. I understand that there is.

<Examples 1-4, Comparative Examples 1 and 2>
Example 1
In Example 1, the carbon (C) grade in the solid content is 0.22 wt%, high pressure air and high pressure oxygen of about 5 MPaG are adjusted to 46.6%, and 426 [ Nm ³ —O ₂ / t—C] was blown in, and the oxygen partial pressure in the vessel was adjusted to 277 kPaG. In addition, about 5 MPaG high pressure water vapor | steam was blown in, and it operated, hold | maintaining at the temperature of 245 degreeC, stirring.

As a result, the ORP (Ag / AgCl electrode standard) of the obtained leaching slurry is suitably maintained at 559 mV, and the amount of sulfuric acid used per ton of dry ore is 226 [kg-H ₂ SO ₄ / t-dry. Solid] and a suitable amount.

(Example 2)
In Example 2, the carbon (C) grade in the solid content is 0.23% by weight, the pressure of high pressure air and high pressure oxygen of about 5 MPaG is adjusted to 47.8%, and 317 [ Nm ³ —O ₂ / t—C] was blown in, and the oxygen partial pressure in the vessel was adjusted to 277 kPaG. In addition, about 5 MPaG high pressure water vapor | steam was blown in, and it operated, hold | maintaining at the temperature of 245 degreeC, stirring.

As a result, the ORP (Ag / AgCl electrode standard) of the obtained leaching slurry is suitably maintained at 518 mV, and the amount of sulfuric acid used per ton of dry ore is 219 [kg-H ₂ SO ₄ / t-dry. Solid] and a suitable amount.

(Example 3)
In Example 3, the carbon (C) grade in the solid content is 0.24 wt%, the pressure of high pressure air and high pressure oxygen of about 5 MPaG is adjusted to 54.7%, and 412 [ Nm ³ —O ₂ / t—C] was blown in, and the oxygen partial pressure in the container was adjusted to 325 kPaG. In addition, about 5 MPaG high pressure water vapor | steam was blown in, and it operated, hold | maintaining at the temperature of 245 degreeC, stirring.

As a result, the ORP (Ag / AgCl electrode standard) of the obtained leaching slurry is suitably maintained at 528 mV, and the amount of sulfuric acid used per ton of dry ore is 232 [kg-H ₂ SO ₄ / t-dry. Solid] and a suitable amount.

Example 4
In Example 4, the same operation as in Example 1 was performed except that high-pressure air and high-pressure oxygen were preliminarily mixed using a commercially available gas mixing device.

  As a result, the same preferable results as in Example 1 were obtained.

(Comparative Example 1)
In Comparative Example 1, the carbon (C) quality in the solid content was set to 0.14% by weight, and only high pressure air of about 5 MPaG (oxygen purity was 20.0%) was blown. Therefore, the amount of oxygen injected was 285 [Nm ³ —O ₂ / tC] per ton of carbon, and the oxygen partial pressure in the container was 101 kPaG. The operation was performed while blowing high-pressure steam of about 5 MPaG and maintaining the temperature at 245 ° C. while stirring.

As a result, although the ORP (Ag / AgCl electrode standard) of the obtained leaching slurry was suitably maintained at 670 mV, the amount of sulfuric acid used per ton of dry ore was 292 [kg-H ₂ SO ₄ / t -Dry Solid]. This is because, in order to maintain the ORP within a suitable range, the carbon (C) grade in the solid content was reduced, and the Mg + Al grade in the ore slurry solid content was increased, and as a result, sulfuric acid was consumed. it is conceivable that.

(Comparative Example 2)
In Comparative Example 2, the carbon (C) grade in the solid content was 0.24% by weight, and only high pressure air of about 5 MPaG (oxygen purity was 20.0%) was blown. Therefore, the amount of oxygen blown was 167 [Nm ³ —O ₂ / tC] per ton of carbon, and the oxygen partial pressure in the container was 90 kPaG. The operation was performed while blowing high-pressure steam of about 5 MPaG and maintaining the temperature at 245 ° C. while stirring.

As a result, the ORP (Ag / AgCl electrode standard) of the obtained leaching slurry decreased to 473 mV. The amount of sulfuric acid in dry ore per ton _{is, 240 [kg-H 2 SO} 4 / t-dry Solid] , and the carbon (C) grade in the solid content was increased compared to Example 3. This is because the oxygen injection amount per ton of carbon was below 200 [Nm ³ —O ₂ / tC], and the ORP was lowered, so that sulfuric acid was regenerated by high-temperature hydrolysis of iron in the autoclave. This is because the amount was reduced and additional sulfuric acid was added to maintain the free acid concentration required for leaching.

(result)
Table 1 below summarizes the results of the treatments in the examples and comparative examples.

As shown in Table 1, the oxygen purity is adjusted to a range of about 45 to 55%, and the oxygen blowing amount (blowing oxygen flow rate) is 310 to 430 [Nm ³ —O ₂ / tC] per ton of carbon amount. In Examples 1 to 4, the ORP was controlled to an average of 535 mV, and it was found that the leaching process could be performed in an optimal ORP environment. Also, the amount of sulfuric acid used is about 227 [kg-H ₂ SO ₄ / t-dry Solid] per ton of dry ore, and the maximum value is 232 [kg-H ₂ SO ₄ / t-dry Solid]. The leaching treatment could be performed without using an excessive amount of sulfuric acid.

On the other hand, in the case of Comparative Example 1 in which only high-pressure air was blown, the oxygen purity was 20.0% and the oxygen blowing amount was 285 [Nm ³ —O ₂ / tC]. Since the carbon quality was as low as 0.21% by weight, the ORP of the leachate was maintained at about 670 mV. However, in Comparative Example 1, since the blending ratio of the low carbon ore species was increased in order to lower the carbon quality in the ore slurry solid content, the magnesium (Mg) and aluminum (Al) quality increased. As a result, these become impurities in high-pressure acid leaching and consume sulfuric acid, so that the amount of sulfuric acid used to maintain a predetermined free sulfuric acid concentration increases significantly, and 270 [kg-H ₂ per ton of dry ore SO ₄ / t-dry Solid].

Further, in the case of Comparative Example 2 in which only a blowing amount of about 167 [Nm ³ —O ₂ / tC] per ton of carbon was ensured for blowing high-pressure air alone, ORP was set to 500 mV. The amount of sulfuric acid regenerated by the high-temperature hydrolysis reaction of iron in the autoclave is reduced, and as a result of adding additional sulfuric acid to maintain the free acid concentration required for leaching, 240 [kg- H ₂ SO ₄ / t-dry Solid].

  As described above, by applying the present invention, a part of the high-pressure air used for maintaining the oxidizing atmosphere is replaced with high-pressure oxygen to increase the oxygen purity and increase the oxygen blowing amount, thereby increasing the ORP of the liquid during leaching. It has been found that a high iron oxidation rate to trivalent iron can be achieved by controlling the temperature within the optimum range.

  In addition, by doing so, the carbon quality in the treated ore can be increased. In other words, it is possible to select an ore blending ratio with a high carbon quality, and it is possible to effectively use finite constituent resources, and it is possible to keep the quality of magnesium, aluminum, and the like that are impurities in acid leaching low. As a result, it is possible to suppress the consumption of sulfuric acid by these impurities in the leaching reaction, reduce the amount used, reduce the chemical cost, and improve the leaching rate of nickel and cobalt with respect to the amount of sulfuric acid used. I understood.

That is, the nickel oxide ore hydrometallurgy method according to the present invention adds sulfuric acid to an ore slurry prepared by slurrying nickel oxide ore, and performs leaching treatment using high-pressure air and high-pressure steam to produce nickel and cobalt. A method of hydrometallizing nickel oxide ore including a step of obtaining a leachate containing, wherein the ore slurry is prepared such that the slurry concentration is 25 to 45% by weight, and in the step of obtaining the leachate, high pressure air and The blowing ratio is adjusted so that the oxygen purity of the blowing gas composed of high-pressure oxygen is 21 to 60%, and the oxygen blowing amount is contained in the ore slurry while maintaining the oxygen purity. Oxidation-reduction potential in leaching treatment as 200 to 600 [Nm ³ —O ₂ / tC] per ton of carbon to be charged (Ag / AgCl standard) Is controlled to 400 to 650 mV.

Claims (5)

A method of hydrometallizing nickel oxide ore, comprising adding sulfuric acid to an ore slurry of nickel oxide ore, leaching using high pressure air and high pressure steam to obtain a leachate containing nickel and cobalt,
In the step of obtaining the leachate, the blowing ratio is adjusted so that the oxygen purity of the blowing gas composed of high-pressure air and high-pressure oxygen is 21 to 60%, and the oxygen blowing amount is maintained while maintaining the oxygen purity. The oxidation-reduction potential (Ag / AgCl standard) in the leaching treatment is 400 to 600 [Nm ³ —O ₂ / tC] per ton of carbon contained in the ore slurry and charged into the process. A method for hydrometallizing nickel oxide ore, characterized by controlling to 650 mV.   2. The method for hydrometallurgy of nickel oxide ore according to claim 1, wherein the ore slurry is prepared so that a slurry concentration is 25 to 45 wt%.   The wet smelting method of nickel oxide ore according to claim 1 or 2, wherein the pH of the leachate obtained in the step of obtaining the leachate is 0.1 to 1.0.   The nickel oxide ore hydrometallurgy method according to any one of claims 1 to 3, wherein the high-pressure air and the high-pressure oxygen are mixed in advance so as to have the oxygen purity.   The method for hydrometallurgy of nickel oxide ore according to any one of claims 1 to 4, wherein carbon dioxide gas generated in the step of obtaining the leachate is released by an automatic pressure control system.

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