WO2011132693A1 - 貯液装置及びその圧力制御方法 - Google Patents
貯液装置及びその圧力制御方法 Download PDFInfo
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- WO2011132693A1 WO2011132693A1 PCT/JP2011/059682 JP2011059682W WO2011132693A1 WO 2011132693 A1 WO2011132693 A1 WO 2011132693A1 JP 2011059682 W JP2011059682 W JP 2011059682W WO 2011132693 A1 WO2011132693 A1 WO 2011132693A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/0318—Processes
- Y10T137/0396—Involving pressure control
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/2931—Diverse fluid containing pressure systems
- Y10T137/3115—Gas pressure storage over or displacement of liquid
- Y10T137/3124—Plural units
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/2931—Diverse fluid containing pressure systems
- Y10T137/3115—Gas pressure storage over or displacement of liquid
- Y10T137/3127—With gas maintenance or application
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/794—With means for separating solid material from the fluid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/8593—Systems
- Y10T137/86187—Plural tanks or compartments connected for serial flow
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/8593—Systems
- Y10T137/86292—System with plural openings, one a gas vent or access opening
Definitions
- the present invention relates to a liquid storage device used in a sulfiding facility for sulfiding a sulfate solution such as a crude nickel sulfate solution to generate a sulfide in a sulfiding step in a nickel oxide ore hydrometallurgical method, and a pressure control method therefor.
- High (Pressure Acid Leach) has attracted attention as a hydrometallurgical method for nickel oxide ore.
- This method does not include dry processing steps such as drying and roasting steps, and consists of a consistent wet process, so that it is advantageous in terms of energy and cost, and nickel / nickel having improved nickel quality to about 50% by weight.
- the cobalt mixed sulfide can be obtained.
- a high-temperature pressure acid leaching method for obtaining a nickel-cobalt mixed sulfide for example, nickel oxide ore is subjected to high-temperature pressure acid leaching, and in addition to nickel and cobalt, crude sulfuric acid containing zinc as an impurity element Step (1) for obtaining a nickel aqueous solution, and introducing the crude nickel sulfate aqueous solution into the sulfurization reactor, adding hydrogen sulfide gas to sulfidize the zinc contained in the crude nickel sulfate aqueous solution, and then separating into solid and liquid Step (2) for obtaining the zinc sulfide formed and the dezinced final solution, and introducing the dezincified final solution into the sulfidation reaction tank and adding hydrogen sulfide gas to be contained in the dezincified final solution (3) a step of sulfiding nickel and cobalt, subsequently introducing the formed slurry into an aeration facility and aeration of
- reaction start solution supply port As the sulfuration reaction tank used in the sulfidation step in the steps (2) and (3) of this high-temperature pressure acid leaching method, a reaction start solution supply port, a slurry discharge port after reaction, and hydrogen sulfide are usually used. It consists of a sealed reaction tank provided with a gas inlet and an exhaust gas outlet for discharging gas in the gas phase as exhaust gas.
- the sulfiding step in the steps (2) and (3) is usually performed in addition to the above-described sulfiding reaction tank, a storage tank or a relay tank (hereinafter simply referred to as a storage tank) for storing slurry and filtrate after the sulfiding reaction.
- Sulfide composed of tanks such as solid-liquid separation tanks, supply pipes for supplying intermediate solutions such as slurries and inert gases to tanks, discharge pipes for discharging from tanks, and pipes connecting tanks Done in the facility.
- Patent Document 1 discloses a method of controlling a metal sulfidation reaction by using hydrogen sulfide gas as a sulfiding agent, adjusting the hydrogen sulfide concentration in the gas phase, and accurately controlling the ORP and pH in the liquid. Is disclosed. Further, Patent Document 2 discloses a method of adding a sulfide seed crystal in order to suppress the adhesion of the generated sulfide to the inner surface of the sulfurization reaction tank at the same time as promoting the sulfurization reaction. Furthermore, Patent Document 3 discloses a method of preferentially separating zinc by adjusting pH and ORP of a nickel sulfate aqueous solution containing cobalt and zinc.
- the hydrogen sulfide gas added for the sulfurization reaction contains about 2 to 3% by volume of inert components such as hydrogen, which is a raw material of the hydrogen sulfide gas production process, and nitrogen mixed in the hydrogen sulfide gas production process. It is.
- the hydrogen sulfide gas used for the sulfidation reaction contains hydrogen, nitrogen, and the like, which are inert components not involved in the sulfidation reaction. Therefore, when the operation of the sulfiding step such as the steps (2) and (3) is continuously performed, the inert component contained in the hydrogen sulfide gas is converted into the sulfidation reaction tank, the slurry after the sulfidation reaction described above, and the like. Is accumulated in the liquid storage tank for storing the liquid, causing the efficiency of the sulfidation reaction to be reduced.
- Patent Document 4 discloses sulfurization by a method of adjusting the volume of the sulfurization reaction tank according to the amount of nickel to be charged or a method of recovering and reusing hydrogen sulfide gas discharged from the sulfurization reaction tank.
- a technique for improving the utilization efficiency of hydrogen gas is disclosed. This technique makes it possible to reduce the amount of hydrogen sulfide used and the amount of alkali used while ensuring a high nickel recovery rate.
- a plurality of liquid storage tanks are provided.
- the slurry after the sulfidation reaction is received, stored, discharged to the solid-liquid separation tank.
- the filtrate after solid-liquid separation is received and repeatedly supplied to the sulfurization reaction tank.
- FIG. 4 is a configuration diagram schematically showing a conventional liquid storage tank 50.
- the storage tank 50 includes a charging pipe 51 for charging the slurry after the sulfidation reaction, a filtrate after the solid-liquid separation, and a discharge pipe 52 for discharging the stored slurry, the filtrate, and the like.
- an inert gas supply pipe 53 that supplies an inert gas (for example, nitrogen gas) that does not participate in the sulfidation reaction, and a gas discharge pipe 54 that discharges the gas inside the liquid storage tank 50.
- an inert gas for example, nitrogen gas
- FIG. 5 is a configuration diagram schematically showing a plurality of liquid storage tanks 50 n provided in a conventional sulfiding facility in which the sulfiding steps in the above steps (2) and (3) are executed.
- each liquid storage tank 50 n has one inert gas supply pipe 53 n and one gas discharge pipe 54 n .
- each inert gas supply pipe 53 n and each gas discharge pipe 54 n are provided with pressure control valves 55 n and 56 n , respectively, and an inert gas supply amount supplied from an inert gas supply facility or emissions into abatement of exhaust gas to each individually controlled to control the pressure in the liquid storage tank 50 n.
- the liquid level in the liquid storage tank 50 n rises and falls due to the entry and exit of slurry, filtrate, and the like with the operation, and the gas level increases and decreases along with the liquid level up and down.
- the pressure in the phase part goes up and down. Therefore, the pressure in the liquid storage tank 50 n is kept constant by adjusting the pressure control valves 55 n and 56 n in the respective liquid storage tanks 50 n as the pressure changes due to the rise or fall of the liquid level. I have to. That is, the pressure is kept constant by discharging part of the gas in the liquid storage tank 50 n as exhaust gas or supplying an inert gas into the liquid storage tank 50 n .
- the exhaust gas contains not only inert components but also residual hydrogen sulfide gas, and the loss of hydrogen sulfide gas occurs due to the exhaust gas exhaust. That is, hydrogen sulfide gas is vaporized from such slurry reservoir to the storage tank 50 n, by vaporized hydrogen sulfide gas is discharged as part of the exhaust gas, the amount of the resulting sulfide be reduced Will end up.
- each of the liquid storage tanks 50 n performs an operation such as exhaust gas discharge by controlling the pressure independently of each other. As a result, the total amount of emissions as exhaust gas will inevitably increase, and the loss of hydrogen sulfide gas will increase.
- the exhaust gas from the liquid storage tank 50 n, in the above step (4), for example, into contact with the alkaline processing liquid abate hydrogen sulfide gas contained in the exhaust gas treatment is essential. Therefore, when the amount of hydrogen sulfide gas discharged as exhaust gas increases, the amount of the alkaline treatment liquid used in step (4) also increases.
- An object of the present invention is to provide a liquid storage device and a pressure control method thereof that reduce the amount of alkali used for the treatment and reduce the operation cost.
- the present inventors have made extensive studies on a method for improving the utilization efficiency of hydrogen sulfide gas with respect to a liquid storage device in a sulfidation facility of a nickel oxide ore hydrometallurgical process.
- the supply efficiency of hydrogen sulfide gas in the sulfidation process is improved by changing the supply of inert gas and the discharge of exhaust gas so that they can be controlled efficiently.
- the present inventors have found that it is possible to improve and reduce the amount of alkaline treatment liquid used to treat the discharged hydrogen sulfide gas, thereby completing the present invention.
- the sulfidation reactor according to the present invention is a liquid storage device used in a sulfidation facility for sulfiding a sulfate solution to produce sulfide in a sulfidation step in a hydrometallurgy method of nickel oxide ore,
- a charging pipe for charging the slurry after the subsequent slurry or solid-liquid separation, a supply / exhaust pipe for supplying inert gas and discharging gas in the gas phase as exhaust gas, and discharging the slurry or filtrate A plurality of storage tanks each having a discharge pipe and a branch pipe in which one end of each of the plurality of storage tanks is connected in parallel to each of the supply and exhaust pipes.
- An exhaust pipe is connected to collect the inert gas supplied to the plurality of reservoirs and the exhaust gas discharged from the plurality of reservoirs, and supply from one end to the plurality of reservoirs Circulate inert gas and
- a pressure control pipe for controlling the internal pressure of the plurality of liquid storage tanks to distribute the exhaust gas discharged from the plurality of liquid storage tanks. And having a pair of pressure control valves before and after sandwiching the connecting portion, the supply of the inert gas to the liquid storage tanks and the liquid storage tanks by the pressure control valves It is characterized by controlling the discharge of exhaust gas from.
- the pressure control method according to the present invention is a pressure control method using the liquid storage device, wherein an inert gas supply facility is connected to one end of the pressure control pipe so that an inert gas can be supplied.
- an inert gas supply facility is connected to one end of the pressure control pipe so that an inert gas can be supplied.
- the inert gas supply facility side The inert gas is supplied to the plurality of storage tanks by adjusting the pressure control valve of the plurality of storage tanks, and the detoxification equipment is used when the internal pressure of the plurality of storage tanks exceeds 1.0 kPa.
- the pressure control valve on the side is adjusted to discharge the gas in the gas phase portion of the plurality of liquid storage tanks as exhaust gas.
- the slurry or filtrate is charged from the charging pipe and discharged from the discharge pipe individually for each liquid storage tank.
- liquid storage device and the pressure control method thereof it is possible to improve the utilization efficiency of hydrogen sulfide gas in the hydrometallurgy method of nickel oxide ore, and the amount of hydrogen sulfide gas used in the sulfidation process
- the operating cost can be greatly reduced by reducing the amount of alkali treatment liquid used for exhaust gas treatment, and its industrial value is extremely high.
- FIG. 1 is a figure showing an example of a process of a hydrometallurgy method of nickel oxide ore by a high temperature pressurization acid leaching method.
- FIG. 2 is a diagram schematically showing the configuration of the liquid storage device according to the present invention.
- FIG. 3 is a diagram schematically showing a liquid storage tank constituting the liquid storage apparatus according to the present invention.
- FIG. 4 is a view schematically showing a conventional liquid storage tank.
- FIG. 5 is a diagram schematically showing a configuration of a plurality of liquid storage tanks provided in a conventional sulfidation facility.
- the liquid storage device and the pressure control method thereof according to the present embodiment are provided in a sulfidation facility that sulfidizes a sulfate solution such as a crude nickel sulfate aqueous solution to generate a sulfide in a sulfidation step in a hydrometallurgy method of nickel oxide ore. It is the liquid storage apparatus used and its pressure control method.
- Nickel oxide ore hydrometallurgical process high-temperature pressure acid leaching process 1-1.
- First step sulfate solution generation step
- Second step zinc sulfide generation step
- Third step Nickel / cobalt mixed sulfide generation step
- Fourth step exhaust gas treatment step
- Nickel oxide ore hydrometallurgical process (high-temperature pressure acid leaching process)> First, prior to describing the liquid storage device and its pressure control method according to the present embodiment, a high-temperature pressurized acid leaching method for a nickel oxide ore hydrometallurgical process that includes a sulfidation process in which they are used in one process. The method will be described as an example.
- FIG. 1 is a diagram showing an outline of a smelting process for smelting nickel oxide ore by a high-temperature pressure acid leaching method.
- a hydrometallurgical method using a high-temperature pressure acid leaching method includes a high-temperature pressure-acid leaching of nickel oxide ore, and a nickel nickel or cobalt solution or a crude nickel sulfate solution containing zinc as an impurity element.
- a step of obtaining a sulfate solution (first step), introducing the sulfate solution into the sulfurization reactor (A), adding hydrogen sulfide gas to sulfidize zinc contained in the sulfate solution, Thereafter, a step of obtaining zinc sulfide and dezincified final solution formed by solid-liquid separation (second step), introducing the dezincified final solution into the sulfurization reactor (B), and adding hydrogen sulfide gas
- the nickel and cobalt contained in the final dezincing solution are sulfided, and then the formed slurry is introduced into an aeration facility to aerate hydrogen sulfide gas, and then solid-liquid separation is performed to obtain a nickel / cobalt mixed sulfide.
- the liquid storage device receives and stores the slurry discharged from the sulfidation reaction tanks (A) and (B) used in the above-described second and third steps, and stores the solid liquid. Processing such as supplying to the separation apparatus and repeatedly supplying the filtrate produced by solid-liquid separation to the sulfurization reaction tanks (A) and (B) is performed.
- the indications (A) and (B) of the sulfidation reaction tank clearly indicate that an individual sulfidation reaction tank is used in each step.
- First Step (Sulfate Solution Generation Step)>
- nickel oxide ore is subjected to high-temperature pressure acid leaching to obtain a sulfate solution containing zinc as an impurity element in addition to nickel and cobalt.
- this first step sulfuric acid is added to a slurry of nickel oxide ore and leached under a high temperature and high pressure of 200 ° C. or higher using an autoclave to obtain a leached slurry;
- a solid-liquid separation process for separating the leach residue containing nickel and cobalt, and adjusting the pH of the leach liquor containing impurity elements together with nickel and cobalt, and neutralizing starch slurry containing impurity elements such as iron and impurity elements
- a neutralization step for producing a sulfate solution which is a sulfurization reaction starting solution from which most of the reaction solution has been removed.
- Leaching step sulfuric acid is added to a slurry of nickel oxide ore and leached under a high temperature and high pressure of 200 ° C. or higher to obtain a leaching slurry.
- the method of high-temperature pressure acid leaching in the leaching step is not particularly limited, and for example, the following method is used. That is, first, nickel oxide ore is slurried to prepare an ore slurry. Next, sulfuric acid is added to the transferred ore slurry, high pressure air is blown as an oxidizer and high pressure steam is blown as a heating source, and the mixture is stirred while being controlled at a predetermined pressure and temperature, and a leach consisting of a leach residue and a leachate. A slurry is formed to obtain a leachate containing nickel and cobalt.
- both the leaching rates of nickel and cobalt can be 90% or more, preferably 95% or more.
- Laterite ores such as limonite or saprolite ore are mainly used.
- Laterite ore usually has a nickel content of 0.5 to 3.0% by mass and is contained as a hydroxide or siliceous clay (magnesium silicate) mineral.
- the iron content is 10 to 50% by mass and is mainly in the form of trivalent hydroxide (goethite, FeOOH), but partly divalent iron is contained in the siliceous clay. .
- the slurry concentration is not particularly limited because it depends greatly on the properties of the nickel oxide ore to be treated.
- the slurry concentration of the leaching slurry is preferably high and is usually adjusted to about 25 to 45% by mass. Is done. If the slurry concentration of the leaching slurry is less than 25% by mass, a large facility is required to obtain the same residence time during leaching, and the amount of acid added to adjust the residual acid concentration also increases. Moreover, the nickel concentration of the obtained leachate also becomes low.
- the operating temperature in the leaching step is not particularly limited, but is preferably 220 to 280 ° C, and more preferably 240 to 270 ° C.
- the temperature in the range of 220 to 280 ° C. most of the iron is fixed as hematite.
- the rate of the high-temperature thermal hydrolysis reaction is slow, so iron remains dissolved in the reaction solution, increasing the load of the subsequent neutralization step for removing iron. Separation from nickel becomes very difficult.
- the amount of sulfuric acid used in the leaching step is not particularly limited, and it is preferable to make it excessive so that iron in the nickel oxide ore is leached.
- it is preferably 200 to 500 kg per ton of ore. If the amount of sulfuric acid added per ton of ore exceeds 500 kg, the sulfuric acid cost increases, which is not preferable.
- the pH of the obtained leachate is preferably adjusted to 0.1 to 1.0 from the filterability of the leach residue containing hematite produced in the solid-liquid separation step.
- Solid-liquid separation step In the solid-liquid separation step, the leaching slurry formed in the leaching step is washed in multiple stages to obtain a leaching solution and leaching residue containing zinc as an impurity element in addition to nickel and cobalt.
- the leaching slurry is mixed with the cleaning liquid, and then solid-liquid separation is performed with a thickener. Specifically, the slurry is first diluted with a cleaning solution, and then the leaching residue is concentrated as a thickener sediment, and the nickel content attached to the leaching residue is reduced according to the degree of dilution.
- thickeners having these functions are connected in multiple stages.
- the multi-stage cleaning in the solid-liquid separation step is not particularly limited, but a continuous alternating current cleaning method (CCD method: Counter-Current Decantation) in which a countercurrent is brought into contact with a cleaning liquid not containing nickel is preferable.
- CCD method Counter-Current Decantation
- the amount of cleaning liquid newly introduced into the system can be reduced, and the recovery rate of nickel and cobalt can be 95% or more.
- the washing liquid used in the solid-liquid separation step is not particularly limited, but preferably does not contain nickel and does not affect this step, and among them, those having a pH of 1 to 3 are preferred. Moreover, it is preferable to use a washing
- the solid content of the residue after settling is not particularly limited, and is preferably 30 to 50% by weight. That is, when the solid content is less than 30% by weight, the amount of adhering water is large and the loss of nickel is large. On the other hand, when the solid ratio exceeds 50% by weight, stirring and liquid feeding become difficult.
- the pH condition in the neutralization step is preferably 4 or less, more preferably 3.2 to 3.8. When the pH exceeds 4, the generation of nickel hydroxide increases.
- the neutralization step when removing the trivalent iron ions remaining in the solution, it is preferable not to oxidize the iron ions present as divalent in the solution, and the solution is oxidized by blowing air or entraining. It is preferable to prevent this.
- the temperature in the neutralization step is preferably 50 to 80 ° C.
- the temperature condition is less than 50 ° C.
- the starch becomes fine and adversely affects the solid-liquid separation process.
- the temperature condition is higher than 80 ° C., the corrosion resistance of the device material is lowered and the energy cost for heating is increased.
- Second Step (Zinc Sulfide Generation Step)>
- hydrogen sulfide gas is added to the sulfate solution containing zinc as an impurity element together with nickel and cobalt obtained in the first step to obtain a zinc sulfide and a dezinced final solution.
- a sulfate solution containing zinc as an impurity element in addition to nickel and cobalt obtained in the first step is introduced into the sulfurization reaction tank (A). To do.
- hydrogen sulfide gas is added into the sulfurization reaction tank to sulfidize the zinc contained in the sulfate solution (sulfurization reaction). Thereafter, a zinc sulfide formed by solid-liquid separation and a dezincing final liquid are obtained.
- This second step is performed in order to prevent zinc from being mixed into the nickel / cobalt mixed sulfide recovered in the subsequent third step. Therefore, it is preferable that the conditions for the sulfidation reaction in the second step are such that zinc is preferentially sulfided over nickel and cobalt by the sulfidation reaction. If the amount of zinc contained in the crude nickel sulfate aqueous solution is so small that it does not pose a problem in quality due to mixing with the nickel / cobalt mixed sulfide produced in the subsequent step, this second step is performed. Can pass.
- the sulfurization reaction in the second step is specifically represented by the following formulas (VI) to (VIII).
- the sulfidation reaction is performed by first dissolving the hydrogen sulfide gas added in the sulfidation reaction tank (A) into water and then converting the hydrogen sulfide into water.
- the dissolution reaction is required.
- the dissolved hydrogen sulfide concentration is generally proportional to the hydrogen sulfide pressure in the gas phase portion of the sulfurization reaction tank according to Henry's law. Therefore, in order to increase the gas-liquid reaction rate, it is important to increase the hydrogen sulfide partial pressure in the gas phase portion.
- the hydrogen sulfide gas to be added contains an inert component such as nitrogen gas, the reaction rate decreases when the inert component accumulates in the sulfurization reaction tank (A).
- the gas in the sulfurization reaction tank (A) in which the inert components are accumulated is periodically discharged by controlling the pressure inside the sulfurization reaction tanks (A) provided in plurality. Specifically, when inert components accumulate in the sulfurization reaction tank (A) and the pressure in the sulfurization reaction tank (A) rises and exceeds a predetermined control pressure, the sulfurization reaction tank (A ) Gas forming the gas phase is discharged from the pressure control valve. As a mechanism for supplying hydrogen sulfide gas into the sulfurization reaction tank (A), the pressure in the sulfurization reaction tank (A) is compared with the supply pressure of hydrogen sulfide gas in order to cause the zinc and hydrogen sulfide gas to react gently. Is controlled to 10% or less.
- the reaction temperature for the sulfurization reaction in the second step is not particularly limited, but is preferably 65 to 90 ° C. Although the sulfidation reaction itself is generally promoted as the temperature rises, if it exceeds 90 ° C., the temperature is increased and the cost is increased, and since the reaction rate is fast, the sulfide is attached to the sulfidation reaction tank (A). May cause problems.
- the method for supplying hydrogen sulfide gas into the sulfidation reaction tank (A) is not particularly limited, but the sulfidation reaction is carried out while mechanically stirring the liquid introduced into the sulfidation reaction tank (A). It is carried out by blowing into the upper space part (gas phase part) or the liquid of the tank (A).
- the liquid storage device constitutes a sulfidation facility together with the sulfidation reaction tank (A) used in the second step.
- the liquid storage device includes a plurality of liquid storage tanks, and some of the liquid storage tanks receive and store the slurry generated by the sulfurization reaction in the sulfurization reaction tank (A).
- the liquid storage tank supplies the stored slurry to the solid-liquid separation tank, and solid-liquid separation is performed in the solid-liquid separation tank. Details of the liquid storage device according to this embodiment will be described later.
- the dezincification final solution obtained in the second step described above is introduced into the sulfurization reactor (B), hydrogen sulfide gas is added, and the dezincification final solution is added.
- the contained nickel and cobalt are sulfided.
- the formed slurry is introduced into an aeration facility, and hydrogen sulfide gas is aerated. Thereafter, solid-liquid separation is performed to obtain a nickel / cobalt mixed sulfide and a smelting waste liquid.
- the aeration of hydrogen sulfide gas from the slurry is performed for the detoxification treatment of the smelting waste liquid.
- a seed crystal made of a sulfide containing nickel and cobalt can be introduced into the sulfidation reaction tank (B) as necessary.
- the ratio of the seed crystal is not particularly limited, but an amount corresponding to 150 to 400% by mass with respect to the amount of nickel and cobalt charged into the sulfurization reactor (B) is preferable.
- the conditions similar to the conditions in the second step described above can be applied to the pressure control in the sulfurization reaction tank (B), the sulfurization reaction temperature, the method of adding hydrogen sulfide gas, and the like.
- the pressure in the sulfurization reaction tank (B) is controlled to 50 to 80% compared to the supply pressure of the hydrogen sulfide gas. Yes.
- the liquid storage device constitutes a sulfidation facility together with the sulfidation reaction tank (B) used in the third step.
- the liquid storage device includes a plurality of liquid storage tanks, and some of the liquid storage tanks are slurries after recovering the slurry generated by the sulfurization reaction in the sulfurization reaction tank (B), nickel and cobalt. Accepts and stores liquid containing hydrogen gas.
- the liquid storage tank supplies the stored slurry to the solid-liquid separation tank, and solid-liquid separation is performed in the solid-liquid separation tank. Details of such a liquid storage device will be described later.
- the liquid storage device used in the third step is a liquid storage device that is different from the liquid storage device that constitutes the sulfiding equipment in the second step.
- the sulfurization reaction tank (A) and the liquid storage device used in the second step described above, and the sulfurization reaction tank (B) and the liquid storage device used in the third step are introduced into the abatement equipment. Then, the exhaust gas introduced into the detoxification facility is detoxified by contacting with the alkali treatment liquid to obtain the detoxified exhaust gas and the detoxification tower waste liquid.
- the abatement equipment used in the fourth step is not particularly limited, and for example, a scrubber or the like that effectively contacts the alkali treatment liquid and the exhaust gas is preferably used.
- the exhaust gas to be treated in the fourth step is exhausted from the sulfidation reaction tanks (A) and (B) and the liquid storage device used in the second and third steps.
- an alkaline treatment liquid is used to detoxify the hydrogen sulfide gas contained in the exhaust gas. Therefore, when there is a lot of hydrogen sulfide gas contained in the exhaust gas, the hydrogen sulfide gas will be discharged wastefully and the amount of alkali treatment liquid used for detoxification will also increase.
- the sulfidation equipment mainly contains a sulfidation reaction tank in which a sulfidation reaction is performed, a slurry storage device for storing the slurry after the sulfidation reaction and the filtrate after solid-liquid separation, an intermediate solution such as slurry and an inert gas. It is comprised by the supply pipe
- a supply port for supplying a reaction start solution such as a sulfate solution, a discharge port for discharging a slurry after reaction, a charging port for charging hydrogen sulfide gas It consists of a sealed reaction tank provided with an exhaust gas outlet for discharging part of the gas as exhaust gas.
- the slurry produced by the sulfidation reaction in the sulfidation reaction tank is charged into the liquid storage device according to the present embodiment and stored.
- the filtrate after solid-liquid separation is inserted and stored.
- the liquid storage apparatus is a liquid storage apparatus used in a sulfiding facility for sulfiding a sulfate solution to generate sulfide in a sulfiding step in a hydrometallurgy method of nickel oxide ore, and hydrogen sulfide
- FIG. 2 is a diagram schematically showing the liquid storage device according to the present embodiment.
- the liquid storage device 10 includes a plurality of slurries generated by sulfiding the sulfate solution in the second and third steps described above or the filtrate after solid-liquid separation.
- Liquid storage tank 11 (11 1 , 11 2 ,... 11 n (hereinafter referred to as “11 n ”)) and inert gas such as nitrogen gas supplied to each liquid storage tank 11 n or each storage
- a collecting pipe 12 that collects the exhaust gas discharged from the liquid tank 11 n and a pressure control pipe 13 that controls the internal pressure of the plurality of liquid storage tanks 11 n by circulating the inert gas while circulating the inert gas.
- liquid storage tank 11 n receives the slurry generated by sulfiding the sulfate solution from the sulfurization reaction tank, stores the slurry, and supplies the stored slurry to the solid-liquid separation tank. Moreover, the filtrate after solid-liquid separation supplied from the solid-liquid separation tank is received and stored, and repeatedly supplied to the sulfurization reaction tank.
- liquid storage apparatus 10 is provided with a plurality of liquid storage tank 11 n, it is used for a variety of purposes for each storage tank 11 n.
- the number of storage tanks 11 n provided in the liquid storage unit 10 is not particularly limited, it can be appropriately selected depending on the production volume and the like.
- FIG. 3 is a configuration diagram schematically showing a liquid storage tank 11 constituting the liquid storage device 10 according to the present embodiment. More specifically, the storage tank 11 supplies a slurry 21 after the sulfurization reaction or a filtrate after the solid-liquid separation, and supplies inert gas and discharges gas in the gas phase as exhaust gas. And a discharge pipe 23 for discharging the stored slurry or filtrate.
- the charging pipe 21 supplies a slurry generated after the sulfate solution is sulfided in the sulfurization reaction tank. Alternatively, the filtrate after the solid-liquid separation in the solid-liquid separation tank is supplied.
- the instrumentation pipe 21 is provided individually for each reservoir 11 n, is supplied slurry Yaro liquid is individually reservoir every 11 n via the instrumentation pipe 21.
- the supply / exhaust pipe 22 sends an inert gas that does not participate in the sulfidation reaction, such as nitrogen gas supplied from an inert gas supply facility, to the liquid storage tank 11, and one of the gases in the gas phase of the liquid storage tank 11.
- the part is discharged as exhaust gas.
- the supply and exhaust pipe 22 are provided separately for each reservoir 11 n, the exhaust gas is discharged together with a separate inert gas is supplied to the reservoir every 11 n via the supply and exhaust pipe 22 .
- the pressure inside the liquid storage tank 11 is controlled by supplying the inert gas into the liquid storage tank 11 and discharging the exhaust gas from the liquid storage tank 11 through the air supply / exhaust pipe 22. It is possible to prevent the liquid storage tank 11 from being damaged.
- the hydrogen sulfide gas supplied to the sulfidation reaction tank for the sulfidation reaction is vaporized from the slurry solution and dissolved in the slurry in the liquid storage tank 11, and has almost reached equilibrium.
- the reservoir device 10 the gas supply and exhaust by linking each supply and exhaust pipe 22 n of each reservoir 11 n to one collecting pipe 12 to be described later set
- the collecting pipe 12 is connected to one pressure control pipe 13 which will be described later. Then, based on the internal pressure of the entire liquid storage tank 11 n , the inert gas is supplied and the exhaust gas is discharged via the pressure control pipe 13.
- the liquid storage device 10 includes a plurality of liquid storage tanks 11 n , it is possible to achieve a state similar to that in which a single liquid storage tank is provided to store slurry or filtrate.
- the amount of exhaust gas to be discharged can be reduced as compared with the conventional case where each liquid storage tank is controlled individually.
- loss of hydrogen sulfide gas to be used for the sulfurization reaction can be suppressed, and hydrogen sulfide gas can be used efficiently.
- the loss of hydrogen sulfide gas can be suppressed, the amount of the alkali treatment liquid used for detoxifying the hydrogen sulfide gas in the fourth step described above can also be reduced.
- the discharge pipe 23 discharges the stored slurry or filtrate.
- the slurry stored in the liquid storage tank 11 is discharged to a solid-liquid separator for performing a solid-liquid separation process.
- the filtrate stored in the storage tank 11 is discharged to a tank or the like for reusing dissolved hydrogen sulfide gas.
- the discharge pipe 23 is provided individually for each reservoir 11 n, the liquid storage tank slurry or filtrate separately for each 11 n is discharged through the exhaust pipe 23.
- the collecting pipe 12 is a branch pipe in which one end has a connecting portion 33 n arranged in parallel with each of the supply and exhaust pipes 22 n of the plurality of liquid storage tanks 11 n.
- the supply / exhaust pipes 22 n of the liquid storage tanks 11 n can be connected to each other through the connection portions 33 n .
- the collecting pipe 12 is connected to a pressure control pipe 13 described later via a connecting portion 30 at the other end.
- reservoir device 10 by providing the collecting pipe 12, the inert gas supplied to the reservoir 11 n via a pressure control line 13 from the inert gas supply equipment set Is done. Further, exhaust gas discharged from each liquid storage tank 11 n to the abatement equipment through the pressure control pipe 13 is collected.
- Pressure control pipe 13 One end of the pressure control pipe 13 is connected to an inert gas supply facility, and the inert gas supplied from the inert gas supply facility is circulated to each liquid storage tank 11 n . Further, the pressure control pipe 13, the other end is connected with the abatement, a portion of the gas in the gas phase of the liquid storage tank 11 n as described above is discharged by flowing into abatement as an exhaust gas.
- the pressure control pipe 13 has a connecting part 30 for connecting the collecting pipe 12 described above, and the collecting pipe 12 is connected via the connecting part 30.
- the pressure control pipe 13 includes a pair of pressure control valves 31 and 32 capable of sealing gas before and after the connecting portion 30 is interposed therebetween. That is, pressure control valves 31 and 32 are provided on the inert gas supply facility side and the detoxification facility side, respectively, across the connecting portion 30 with the collecting pipe 12. Thereby, by adjusting the pressure control valve 31 on the inert gas supply facility side, the supply amount of the inert gas supplied from the inert gas supply facility to the liquid storage tank 11 n is adjusted, and the liquid storage tank 11 is adjusted. Control the pressure of n . Further, by adjusting the abatement side pressure control valve 32 to adjust the discharge amount to the abatement of gases that constitutes a part of the gas phase of the liquid storage tank 11 n, the liquid storage tank 11 n To control the pressure.
- the pressure control pipe 13 includes a pressure gauge for measuring the pressure inside the plurality of liquid storage tanks 11 n constituting the liquid storage apparatus 10 according to the present embodiment.
- a pressure gauge for measuring the pressure inside the plurality of liquid storage tanks 11 n constituting the liquid storage apparatus 10 according to the present embodiment.
- the reservoir apparatus 10 According to the reservoir apparatus 10 according to the present embodiment having the above structure, and is discharged from the supply amount and the liquid storage tank 11 n of the inert gas supplied to each liquid reservoir 11 n in controlling the pressure reservoir within 11 n based on the emissions of the exhaust gas, it is possible to comprehensively manage the pressure of a plurality of reservoir 11 n. That is, in the liquid storage tank 11 n, the inert gas is supplied and the exhaust gas from the storage tank 11 n done by one supply and exhaust pipe 22 n respectively, supply and exhaust pipes of the respective storage tanks 11 n the 22 n are gathered by the collecting pipe 12, by controlling the supply and discharge via a pressure control line 13 can be controlled comprehensively manage the pressure inside the plurality of liquid storage tank 11 n .
- an inert gas supply pipe and an exhaust gas discharge pipe are provided in each of the plurality of storage tanks, and the inert gas supply and exhaust gas are controlled based on independent pressure control for each storage tank.
- the amount of hydrogen sulfide gas discharged as exhaust gas can be suppressed.
- each liquid storage tank Part of the gas in the gas phase is discharged as exhaust gas, and the pressure inside each reservoir is lowered.
- the exhaust gas contains, for example, hydrogen sulfide gas evaporated from the slurry solution. Therefore, when exhaust gas is discharged based on the pressure control for each liquid storage tank, a predetermined amount of exhaust gas is discharged from each of the plurality of liquid storage tanks, so it is included in the exhaust gas discharged from the entire liquid storage device. The total amount of hydrogen sulfide gas that is generated is inevitably increased.
- the supply / exhaust pipes 22 n of the liquid storage tanks 11 n that supply the inert gas and discharge the exhaust gas are gathered, and the pressure control pipe 13 is connected. through, since so as to control the pressure based on the pressure of a plurality of storage tanks 11 n, it is unnecessary to independently exhaust gas from the reservoir 11 n are discharged.
- the total amount of hydrogen sulfide gas in the exhaust gas discharged from the entire liquid storage device 10 can be reduced without wastefully discharging the hydrogen sulfide gas from each liquid storage tank 11 n . Hydrogen sulfide gas is maintained without being discharged in this way the liquid storage tank 11 n.
- each provided with a discharge pipe 23 n for discharging the liquid storage tank 11 n slurry Yaro liquid was charged pipe 21 n or reservoir which is charged with slurry Yaro liquid separately for each individual in each reservoir every 11 n
- the utilization efficiency of the hydrogen sulfide gas can be enhanced.
- the liquid surface of the liquid storage tank 11 n is up and down, the savings the pressure inside the liquid tank 11 n are different between the liquid storage tank 11 n, it becomes not constant.
- the liquid storage apparatus 10 according to this embodiment even if a difference in internal pressure between the reservoir 11 n, between the reservoir 11 n, via a collecting pipe 12 exhaust gas Can be dispersed.
- the amount of the alkaline treatment liquid used for the detoxification treatment can also be efficiently reduced. That is, in the fourth step described above, the exhaust gas discharged from the liquid storage device 10 is also detoxified. However, when the amount of hydrogen sulfide gas is large in the exhaust gas, the alkali treatment liquid used for the detoxification treatment is removed. The amount used also increases. According to the liquid storage device 10 according to the present embodiment, as described above, the amount of discharged hydrogen sulfide gas can be reduced, so that the amount of alkaline treatment liquid used for the detoxification treatment can be effectively reduced. Can be reduced.
- each of the plurality of liquid storage tanks is provided with an inert gas supply pipe and an exhaust gas discharge pipe separately and a pressure control valve, and the pressure in the liquid storage tank is individually controlled for each liquid storage tank.
- the number of points used such as pipes and valves can be reduced. Thereby, while reducing the operating cost, the utilization efficiency of the hydrogen sulfide gas can be improved and the usage amount of the alkaline treatment liquid can be reduced, thereby improving the operation efficiency.
- the inert gas can be supplied by connecting an inert gas supply system to the one end of the pressure control pipe 13, the liquid storage tank 11 n on the other end It is possible to discharge exhaust gas by connecting a detoxification facility for treating the exhaust gas.
- the pressure control method according to the present embodiment uses the liquid storage device 10, and when the internal pressure of the plurality of liquid storage tanks 11 n becomes less than 0.5 kPa, the inert gas supply facility side
- the pressure control valve 31 is adjusted to supply an inert gas such as nitrogen gas to the plurality of liquid storage tanks 11 n via the pressure control pipe 13.
- an inert gas such as nitrogen gas
- the gas flowing through each liquid storage tank 11 n is collected by the collecting pipe 12 and the gas is distributed between the liquid storage tanks 11 n .
- the pressure inside the liquid storage tank 11 n is controlled to the above-described range via the pressure control pipe 13.
- a pressure detection unit that detects the pressure of each liquid storage tank 11 n based on a measurement value by a pressure gauge provided in the pressure control pipe 13, and the pressure detection unit And a control unit for controlling the pair of pressure control valves 31 and 32 provided in the pressure control pipe 13 based on the pressure of each liquid storage tank 11 n detected by the automatic pressure control of the liquid storage device 10. You may make it control.
- the pressure detection unit detects whether or not the pressure of each liquid storage tank 11 n constituting the liquid storage device 10 is less than 0.5 kPa based on a pressure gauge provided in the pressure control pipe 13. . And when the detected pressure is less than 0.5 kPa, the detection signal is supplied to a control part. The control unit adjusts the pressure control valve 31 on the inert gas supply facility side in accordance with the received detection signal to distribute the inert gas to the liquid storage tank 11 n and continues until the pressure becomes 0.5 kPa or more. .
- the pressure detector the pressure of the liquid storage tank 11 n detects whether 1.0kPa greater.
- the detection signal is supplied to the control unit.
- the control unit adjusts the pressure control valve 32 on the side of the detoxifying equipment according to the received detection signal to discharge the exhaust gas from the liquid storage tank 11 n and continues until the pressure becomes 1.0 kPa or less.
- the liquid storage apparatus 10 is a storage apparatus used in a sulfidation facility that sulfidizes a sulfate solution to generate sulfides in a sulfidation step in a wet smelting method of nickel oxide ore.
- a plurality of storage tanks 11 n for storing the slurry produced by sulfidation of the sulfate solution in the above-described second and third steps or the filtrate after solid-liquid separation; reservoir 11 and collection tube 12 to set the exhaust gas discharged from the inert gas or the liquid reservoir 11 n are supplied to n, by circulating the exhaust gas with circulating inert gas plurality of storage tanks 11 and a pressure control pipe 13 for controlling the pressure inside n .
- the pressure control pipe 13 is connected to the collecting pipe 12 via a connecting portion 30, and is provided with a pair of pressure control valves 31 and 32 before and after sandwiching the connecting portion 30.
- the pressure control method of the liquid storage device is an example in which an inert gas supply facility is connected to one end of the pressure control pipe 13 so that an inert gas can be supplied and exhaust gas is processed at the other end. If the internal pressure of the plurality of storage tanks 11n becomes less than 0.5 kPa, the pressure control valve 31 on the inert gas supply equipment side is adjusted if exhaust gas can be discharged by connecting harmful equipment. supplying an inert gas to a plurality of reservoir 11 n, when the internal pressure of the plurality of liquid storage tank 11 n is greater than 1.0kPa adjusts the pressure control valve 32 of the abatement side the gas phase of the gas of the plurality of liquid storage tank 11 n discharged as exhaust gas Te.
- liquid storage device 10 According to such a liquid storage device 10 and its pressure control method, it is possible to reduce the discharge of hydrogen sulfide gas that has been exhausted more than necessary, and to improve the utilization efficiency of hydrogen sulfide gas. As a result, the amount of hydrogen sulfide gas used in the sulfidation step and the amount of alkali treatment liquid used for exhaust gas treatment can be reduced to greatly reduce the operating cost.
- the utilization efficiency of hydrogen sulfide gas was measured based on the usage amount of the alkaline treatment liquid used in the fourth step described above. Note that when the amount of hydrogen sulfide gas discharged from the liquid storage tank is large, the amount of alkali treatment liquid used to detoxify hydrogen sulfide gas also increases. This means that the loss of hydrogen gas as exhaust gas has been reduced.
- Example 1 The operation for 4 months was carried out by the sulfidation equipment provided with the liquid storage device 10 according to the present invention.
- a sodium hydroxide solution was used as the alkali treatment liquid for exhaust gas treatment.
- the basic unit of sodium hydroxide was calculated by the following formula.
- the nickel production amount in the formula is a conversion amount as a nickel component in the nickel / cobalt mixed sulfide produced in the fourth step.
- Sodium hydroxide basic unit amount of sodium hydroxide used (t) / nickel production (t)
- Example 1 the amount of sodium hydroxide solution used was 0.34 in basic units.
- Example 1 The same operation as in Example 1 was performed except that a sulfidation facility equipped with a conventional liquid storage device was used. Note that the amount of alkali used was also measured in the same manner as in the examples.
- the usage amount of the alkaline processing liquid is reduced per unit. It was possible to reduce about 60%.
- the liquid storage apparatus and the pressure control method thereof provide a nickel recovery rate for nickel / cobalt mixed sulfide in a hydrometallurgical method of nickel oxide ore using a high-temperature pressure acid leaching method. While maintaining a high yield, the utilization efficiency of hydrogen sulfide gas can be improved, and it is suitable as a hydrometallurgical method of nickel oxide ore that can reduce operating costs.
- the present invention is not limited to a wet refining plant for nickel oxide ore, but can also be applied to a slurry including hard particles and a plant with generation of precipitates that easily adhere to the surface of the apparatus, and its industrial value is high.
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Abstract
Description
本出願は、日本国において2010年4月22日に出願された日本特許出願番号特願2010-098772を基礎として優先権を主張するものであり、これらの出願を参照することにより、本出願に援用される。
1.ニッケル酸化鉱石の湿式製錬方法(高温加圧酸浸出法)
1-1.第1の工程(硫酸塩溶液生成工程)
1-2.第2の工程(亜鉛硫化物生成工程)
1-3.第3の工程(ニッケル・コバルト混合硫化物生成工程)
1-4.第4の工程(排ガス処理工程)
2.硫化設備について
2-1.貯液装置
2-2.貯液装置の圧力制御反応
3.まとめ
4.実施例
先ず、本実施の形態に係る貯液装置及びその圧力制御方法について説明するに先立ち、それらが使用される硫化工程を一工程に含む、ニッケル酸化鉱石の湿式製錬方法について、高温加圧酸浸出法を一例として説明する。
第1の工程では、ニッケル酸化鉱石を高温加圧酸浸出し、ニッケル及びコバルトのほか、不純物元素として亜鉛を含有する硫酸塩溶液を得る。
浸出工程では、ニッケル酸化鉱石のスラリーに硫酸を添加し、200℃以上の高温高圧下で浸出させて、浸出スラリーを得る。
MO+H2SO4 ⇒ MSO4+H2O ・・・(I)
(式中Mは、Ni、Co、Fe、Zn、Cu、Mg、Cr、Mn等を表す。)
2FeOOH+3H2SO4 ⇒ Fe2(SO4)3+4H2O ・・・(II)
FeO+H2SO4 ⇒ FeSO4+H2O ・・・(III)
《高温加水分解反応》
2FeSO4+H2SO4+1/2O2 ⇒ Fe2(SO4)3+H2O ・・(IV)
Fe2(SO4)3+3H2O⇒ Fe2O3+3H2SO4 ・・・(V)
固液分離工程では、上述の浸出工程で形成された浸出スラリーを多段洗浄し、ニッケル及びコバルトのほか、不純物元素として亜鉛を含有する浸出液と浸出残渣とを得る。
中和工程では、固液分離工程にて生成した、ニッケル及びコバルトとともに不純物元素を含有する浸出液の酸化を抑制しながらpHを調整し、3価の鉄を含む中和澱物スラリーと、不純物の大部分を除去した硫化反応始液である粗硫酸ニッケル溶液等の硫酸塩溶液を生成する。これによって、高温高圧酸浸出工程で用いた過剰の酸の中和を行うとともに、溶液中に残留する3価の鉄イオンの除去を行う。
第2の工程では、第1の工程で得られた、ニッケル及びコバルトとともに不純物元素として亜鉛を含有する硫酸塩溶液に硫化水素ガスを添加して、亜鉛硫化物と脱亜鉛終液とを得る。
H2S(g)+H2O ⇒ H2S in aq ・・・(VI)
H2S⇒H++HS-⇒2H++S2- ・・・(VII)
M2++2H++S2-⇒2H++MS↓ ・・・(VIII)
(なお、式中Mは、Zn等を表す。)
第3の工程では、硫化水素ガスを添加して、第2の工程で得られた脱亜鉛終液中に含有されるニッケル及びコバルトを硫化し、ニッケル・コバルト混合硫化物と製錬廃液を得る。
第4の工程では、第2の工程及び第3の工程にて排出された排ガスをアルカリ処理液によって処理する。
次に、上述したニッケル酸化鉱石の湿式製錬方法の第2の工程及び第3の工程において使用される硫化設備について説明する。硫化設備は、主に、硫化反応が行われる硫化反応槽と、硫化反応後のスラリーや固液分離後のろ液を貯液する貯液装置と、スラリー等の中間溶液や不活性ガス等をタンクへ供給する供給管及びタンクから排出する排出管と、また硫化反応槽と貯液装置とを連結する配管等によって構成されている。
本実施の形態に係る貯液装置は、ニッケル酸化鉱石の湿式製錬方法における硫化工程において、硫酸塩溶液を硫化させて硫化物を生成させる硫化設備に用いられる貯液装置であって、硫化水素ガスの利用効率を向上させることが可能な貯液装置である。この貯液装置によれば、硫化水素ガスの使用量を減少させるとともに、上述した第4の工程における硫化水素ガスを含んだ排ガス処理に用いるアルカリ処理液の使用量を減少させることができる。
貯液槽11nは、硫酸塩溶液を硫化させることにより生成したスラリーを硫化反応槽から受け入れ、そのスラリーを貯液するとともに、貯液したスラリーを固液分離槽に供給する。また、固液分離槽から供給された固液分離後のろ液を受け入れて貯液し、繰り返し硫化反応槽に供給する。このように、本実施の形態に係る貯液装置10は、貯液槽11nを複数備えており、各貯液槽11n毎に多様な目的のために使用される。貯液装置10に備えられる貯液槽11nの数は、特に限定されるものでなく、生産量等により適宜選択することができる。
集合管12は、後述する圧力制御配管13を介して供給され各貯液槽11nに供給する不活性ガスの流通路になるとともに、各貯液槽11nから排出され圧力制御配管13を介して除害設備に送られる排ガスの流通路になる。
圧力制御配管13は、一端が不活性ガス供給設備と接続され、不活性ガス供給設備から供給される不活性ガスを各貯液槽11nに流通させる。また、圧力制御配管13は、他端が除害設備と接続され、上述した各貯液槽11nの気相中のガスの一部を排ガスとして除害設備へと流通させ排出する。
具体的に、本実施の形態に係る貯液装置10の圧力制御方法について説明する。上述のように、貯液装置10を構成する各貯液槽11nでは、各個別にスラリーやろ液等が装入され、また排出される。これにより、各貯液槽11nにおいて、スラリーやろ液の装入や排出に伴い、貯液槽11nの内部の液面が上下し、貯液槽11n内部の圧力も上下することとなる。
以上説明したように、本実施の形態に係る貯液装置10は、ニッケル酸化鉱石の湿式製錬方法における硫化工程において、硫酸塩溶液を硫化させて硫化物を生成させる硫化設備に用いられる貯液装置10であって、上述の第2及び第3の工程にて硫酸塩溶液が硫化されて生成したスラリー又は固液分離後のろ液を貯液する複数の貯液槽11nと、各貯液槽11nに供給される不活性ガス又は各貯液槽11nから排出される排ガスを集合させる集合管12と、不活性ガスを流通させるとともに排ガスを流通させて複数の貯液槽11nの内部の圧力を制御する圧力制御配管13とを備える。また、圧力制御配管13には、集合管12と連結部30を介して連結し、その連結部30を挟んだ前後に一対の圧力制御バルブ31,32が備えられている。そして、この貯液装置10においては、圧力制御配管13に備えられた一対の圧力制御バルブ31,32によって、各貯液槽11nへの不活性ガスの供給及び各貯液槽11nからの排ガスの排出を制御する。
以下、本発明の具体的な実施例について説明する。なお、下記のいずれかの実施例に本発明の範囲が限定されるものではない。
本発明に係る貯液装置10を備えた硫化設備によって、4ヶ月の操業を実施した。排ガス処理用のアルカリ処理液としては、水酸化ナトリウム溶液を使用した。
水酸化ナトリウム原単位=水酸化ナトリウム使用量(t)/ニッケル生産量(t)
従来の貯液装置を備えた硫化設備を使用した以外は、実施例1と同様に操業した。なお、アルカリ使用量の測定も、実施例と同様にして行った。
Claims (5)
- ニッケル酸化鉱石の湿式製錬方法における硫化工程において、硫酸塩溶液を硫化させて硫化物を生成させる硫化設備に用いられる貯液装置であって、
硫化反応後のスラリー又は固液分離後のろ液を装入する装入管と、不活性ガスを供給するとともに気相中のガスを排ガスとして排出する給排気管と、該スラリー又はろ液を排出する排出管とを有する複数の貯液槽と、
一端が上記複数の貯液槽の各給排気管との接続部を並列に配置した分岐管となっており、該接続部を介して該各給排気管を接続させて、該複数の貯液槽に供給する上記不活性ガス及び該複数の貯液槽から排出される上記排ガスを集合させる集合管と、
一端から上記複数の貯液槽へ供給する不活性ガスを流通させるとともに、他端へ上記複数の貯液槽から排出される上記排ガスを流通させ、該複数の貯液槽の内部の圧力を制御する圧力制御配管とを備え、
上記圧力制御配管は、上記集合管の他端と連結部を介して連結しており、該連結部を挟んだ前後に一対の圧力制御バルブを有し、該圧力制御バルブによって、上記各貯液槽への上記不活性ガスの供給及び該各貯液槽からの排ガスの排出を制御することを特徴とする貯液装置。 - 上記圧力制御配管は、上記複数の貯液槽の内部の圧力を測定する圧力計を有することを特徴とする請求項1記載の貯液装置。
- 上記不活性ガスは、窒素ガスであることを特徴とする請求項1又は2記載の貯液装置。
- 上記請求項1乃至3の何れか1項記載の貯液装置を用いた圧力制御方法であって、
上記圧力制御配管の一端に不活性ガス供給設備を接続して不活性ガスを供給可能とし、他端に上記排ガスを処理する除害設備を接続して該排ガスを排出可能とし、
上記複数の貯液槽の内部の圧力が0.5kPa未満となった場合には、上記不活性ガス供給設備側の上記圧力制御バルブを調整して該複数の貯液槽に上記不活性ガスを供給し、
上記複数の貯液槽の内部の圧力が1.0kPaより大きくなった場合には、上記除害設備側の上記圧力制御バルブを調整して該複数の貯液槽の気相部のガスを排ガスとして排出することを特徴とする圧力制御方法。 - 上記複数の貯液槽では、各貯液槽毎に個別に、スラリー又はろ液が上記装入管から装入されるとともに上記排出管から排出されることを特徴とする請求項4記載の圧力制御方法。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2808299A4 (en) * | 2012-01-17 | 2015-11-18 | Sumitomo Metal Mining Co | GAS HYDROGEN SULFIDE PRODUCTION FACILITY AND METHOD FOR RECOVERING AND USING HYDROGEN SULFIDE GAS RESIDUE |
EP2933235A4 (en) * | 2012-12-11 | 2016-08-17 | Sumitomo Metal Mining Co | TREATMENT DEVICE AND PROCESSING METHOD FOR STERILE SOLUTION CONTAINING HYDROGEN SULFIDE |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5360243B2 (ja) * | 2012-02-01 | 2013-12-04 | 住友金属鉱山株式会社 | 鉱石スラリー製造工程におけるシックナー装置及びその固体成分率制御方法 |
JP5644878B2 (ja) | 2013-01-21 | 2014-12-24 | 住友金属鉱山株式会社 | 固液分離処理方法、並びにニッケル酸化鉱石の湿式製錬方法 |
US20140345700A1 (en) * | 2013-05-22 | 2014-11-27 | Hamilton Sundstrand Corporation | Pressure monitoring system for a fuel tank and method |
JP5692313B2 (ja) * | 2013-09-02 | 2015-04-01 | 住友金属鉱山株式会社 | 鉱石スラリー製造工程におけるシックナー装置及びその固体成分率制御方法 |
JP5783223B2 (ja) * | 2013-11-01 | 2015-09-24 | 住友金属鉱山株式会社 | 鉱石スラリー製造設備および鉱石スラリー製造方法 |
EP3128018A4 (en) * | 2014-12-05 | 2017-04-26 | Sumitomo Metal Mining Co., Ltd. | Apparatus for producing ore slurry and process for producing ore slurry |
JP6696189B2 (ja) * | 2016-01-28 | 2020-05-20 | 住友金属鉱山株式会社 | 残存硫化水素の除去方法 |
JP6738560B2 (ja) * | 2016-09-23 | 2020-08-12 | 住友金属鉱山株式会社 | 密閉型ms反応槽のレベル計の校正方法と液面レベル変動の検出方法、並びにそれらを用いた監視システム |
JP6862970B2 (ja) * | 2017-03-21 | 2021-04-21 | 住友金属鉱山株式会社 | 硫化物の製造設備 |
JP6919408B2 (ja) * | 2017-08-17 | 2021-08-18 | 住友金属鉱山株式会社 | 反応容器 |
JP7110578B2 (ja) * | 2017-10-23 | 2022-08-02 | 住友金属鉱山株式会社 | オートクレーブの制御システム、及び制御方法 |
US11761582B2 (en) * | 2019-09-05 | 2023-09-19 | Dhf America, Llc | Pressure regulation system and method for a fluidic product having particles |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010031302A (ja) * | 2008-07-25 | 2010-02-12 | Sumitomo Metal Mining Co Ltd | ニッケル酸化鉱石の湿式製錬方法 |
JP2010031341A (ja) * | 2008-07-31 | 2010-02-12 | Sumitomo Metal Mining Co Ltd | ニッケル酸化鉱石の湿式製錬方法 |
JP2010059489A (ja) * | 2008-09-04 | 2010-03-18 | Sumitomo Metal Mining Co Ltd | オートクレーブの圧力調整方法 |
JP2010098772A (ja) | 2006-10-03 | 2010-04-30 | Ntt Docomo Inc | 無線基地局 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2020325A (en) * | 1933-12-15 | 1935-11-12 | New Jersey Zinc Co | Method of producing precipitates |
US2548003A (en) * | 1945-03-01 | 1951-04-10 | American Viscose Corp | Method and apparatus for handling unstable chemical dispersions |
US2617765A (en) * | 1949-06-18 | 1952-11-11 | Corn Prod Refining Co | Air dome control for ion exchange units |
US2947318A (en) * | 1957-08-26 | 1960-08-02 | Sun Oil Co | Automatic tank switching system |
US3035888A (en) * | 1960-10-31 | 1962-05-22 | Universal Oil Prod Co | Process and apparatus for obtaining a constant head of liquid |
US4331635A (en) * | 1972-03-07 | 1982-05-25 | Atlantic Richfield Company | Recovery of copper and/or nickel and/or zinc |
US3797744A (en) * | 1972-11-20 | 1974-03-19 | W Smith | Portable cleaning and sanitizing system |
US4019524A (en) * | 1973-08-27 | 1977-04-26 | Phillips Petroleum Company | Use of equalization chamber in discontinuous venting of vessel |
US3988416A (en) * | 1974-06-13 | 1976-10-26 | Kennecott Copper Corporation | Elevated pressure operation in the cuprion process |
US4110400A (en) * | 1977-08-01 | 1978-08-29 | Amax Inc. | Selective precipitation of nickel and cobalt sulfides from acidic sulfate solution |
US4629502A (en) * | 1984-10-25 | 1986-12-16 | Kamyr, Inc. | Pressurized reaction of refractory ores with heat recovery |
US4859375A (en) * | 1986-12-29 | 1989-08-22 | Air Products And Chemicals, Inc. | Chemical refill system |
JP2846891B2 (ja) * | 1988-06-03 | 1999-01-13 | 東京エレクトロン株式会社 | 処理装置 |
US5250273A (en) * | 1990-01-18 | 1993-10-05 | Canadian Liquid Air Ltd - Air Liquide Canada Ltee | Hydrometallurgical leaching process and apparatus |
US5148945B1 (en) * | 1990-09-17 | 1996-07-02 | Applied Chemical Solutions | Apparatus and method for the transfer and delivery of high purity chemicals |
US5052426A (en) * | 1991-01-16 | 1991-10-01 | The United States Of America As Represented By The United States Department Of Energy | System for pressure letdown of abrasive slurries |
US5607000A (en) * | 1994-10-31 | 1997-03-04 | Motorola, Inc. | Hazardous material liquid dispensing system and method |
TW382749B (en) * | 1996-12-24 | 2000-02-21 | Tokyo Electron Ltd | Liquid supplying device |
US7100631B2 (en) * | 2002-11-06 | 2006-09-05 | Atomic Energy Council-Institute Of Nuclear Energy Research | Multifunction passive and continuous fluid feeding system |
CN102502132A (zh) * | 2011-10-09 | 2012-06-20 | 北京七星华创电子股份有限公司 | 液体存储装置 |
-
2010
- 2010-04-22 JP JP2010098772A patent/JP4888580B2/ja active Active
-
2011
- 2011-04-20 EP EP11772026.8A patent/EP2562275B1/en not_active Not-in-force
- 2011-04-20 US US13/639,793 patent/US9139890B2/en not_active Expired - Fee Related
- 2011-04-20 AU AU2011243578A patent/AU2011243578B2/en not_active Ceased
- 2011-04-20 WO PCT/JP2011/059682 patent/WO2011132693A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010098772A (ja) | 2006-10-03 | 2010-04-30 | Ntt Docomo Inc | 無線基地局 |
JP2010031302A (ja) * | 2008-07-25 | 2010-02-12 | Sumitomo Metal Mining Co Ltd | ニッケル酸化鉱石の湿式製錬方法 |
JP2010031341A (ja) * | 2008-07-31 | 2010-02-12 | Sumitomo Metal Mining Co Ltd | ニッケル酸化鉱石の湿式製錬方法 |
JP2010059489A (ja) * | 2008-09-04 | 2010-03-18 | Sumitomo Metal Mining Co Ltd | オートクレーブの圧力調整方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2808299A4 (en) * | 2012-01-17 | 2015-11-18 | Sumitomo Metal Mining Co | GAS HYDROGEN SULFIDE PRODUCTION FACILITY AND METHOD FOR RECOVERING AND USING HYDROGEN SULFIDE GAS RESIDUE |
US9480956B2 (en) | 2012-01-17 | 2016-11-01 | Sumitomo Metal Mining Co., Ltd. | Hydrogen sulfide gas production plant and method for recovering and using waste hydrogen sulfide gas |
EP2933235A4 (en) * | 2012-12-11 | 2016-08-17 | Sumitomo Metal Mining Co | TREATMENT DEVICE AND PROCESSING METHOD FOR STERILE SOLUTION CONTAINING HYDROGEN SULFIDE |
US9731980B2 (en) | 2012-12-11 | 2017-08-15 | Sumitomo Metal Mining Co., Ltd. | Processing device and processing method for hydrogen-sulphide-containing barren solution |
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