JP2015127053A - Treatment method and treatment apparatus for barren solution including hydrogen sulfide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treatment method and a treatment apparatus for barren solution including hydrogen sulfide, for efficiently removing hydrogen sulfide from the barren solution.SOLUTION: The treatment method for barren solution including hydrogen sulfide uses an aeration tank that comprises: a reaction container 110 of a vertical cylindrical shape; an agitation blade 120 provided in the reaction container 110; a circular ring-shaped aeration tube 130 having a plurality of blowing-out ports 131 provided in a bottom of the reaction container 110; and a baffle plate 151. Aeration is performed in the aeration tank by spraying aeration gas into the reaction container 110 from the plurality of blowing-out ports 131 of the aeration tube 130 while agitating liquid by rotation of the agitation blade 120, and the flow of the aeration gas is straightened by the baffle plate 151.

Description

  The present invention relates to a processing method and a processing apparatus for a poor liquid containing hydrogen sulfide, such as a process liquid after sulfiding treatment of a nickel oxide ore plant.

  Conventionally, as a hydrometallurgical method for recovering valuable metals such as nickel and cobalt from nickel oxide ores with low nickel content typified by limonite ore, high-temperature pressure acid leaching using sulfuric acid (HPAL: High Pressure Acid) (Leaching) method is known.

  For example, in the high-pressure acid leaching method for obtaining a nickel-cobalt mixed sulfide, as shown in FIG. 4, the pretreatment step (1), the leaching step (2), the solid-liquid separation step (3), The sum process (4), the dezincification process (5), the sulfurization process (6), and the detoxification process (7) are included (for example, refer patent document 1).

  In the pretreatment step (1), the nickel oxide ore is crushed and classified into a slurry.

  In the leaching step (2), sulfuric acid is added to the slurry obtained in the pretreatment step (1), and the mixture is stirred at 220 to 280 ° C. to perform high-temperature pressure acid leaching to obtain a leaching slurry.

  In the solid-liquid separation step (3), the leaching slurry obtained in the leaching step (2) is subjected to solid-liquid separation to obtain a leachate containing nickel and cobalt (hereinafter referred to as “crude nickel sulfate aqueous solution”) and the leaching residue. obtain.

  In the neutralization step (4), the crude nickel sulfate aqueous solution obtained in the solid-liquid separation step (3) is neutralized.

  In the zinc removal step (5), hydrogen sulfide gas is added to the crude nickel sulfate aqueous solution neutralized in the neutralization step (4) to precipitate and remove zinc as zinc sulfide.

  In the sulfidation step (6), hydrogen sulfide gas is added to the final zinc removal solution obtained in the dezincification step (5) to obtain a nickel / cobalt composite sulfide and a nickel poor solution. In the detoxification step (7), the heavy metal was solidified as a hydroxide and removed by the final neutralization treatment, so that the leach residue generated in the solid-liquid separation step (3) and the sulfidation step (6) occurred. Detoxify nickel poor solution.

  In general, nickel oxide ore contains many kinds of heavy metals, and is dissolved under high temperature and high pressure conditions using sulfuric acid. Collect the necessary metals. In the sulfurization reaction, hydrogen sulfide gas or a salt such as sodium hydrogen sulfide or sodium sulfide is used, but unreacted sulfide remains after the sulfurization step.

  When hydrogen sulfide gas is used for the sulfurization reaction, unreacted hydrogen sulfide gas is dissolved in the liquid after the reaction. Even when a salt such as sodium hydrogen sulfide or sodium sulfide is used, depending on the state of the solution Hydrogen sulfide gas is generated. The solution after sulfidation is reused or drained in the process (see, for example, Patent Document 2).

  If hydrogen sulfide gas is generated in these processes, it is not desirable from the viewpoint of occupational hygiene and the environment.

  Conventionally, as a method of removing dissolved hydrogen sulfide in a solution (poor liquid) after a sulfidation reaction, a large amount of the leached nickel oxide ore slurry is added to the sulfurized poor liquid after leaching. There is known a method of reducing the concentration of dissolved hydrogen sulfide by oxidizing hydrogen sulfide to sulfur using the reduction action of trivalent iron present in the steel.

  However, when the above-described method is used, it is necessary to repeat the slurry after addition of acid or leaching, and since dissolved hydrogen sulfide is still present in the solution after the reaction, further reduction of dissolved hydrogen sulfide is achieved. Is requested.

JP 2011-225908 A JP-A-2005-350766 Japanese Patent Application Laid-Open No. 08-071585 JP-A-10-258222

  The present invention has been made in view of such a situation, and the object of the present invention is, for example, in a solution containing hydrogen sulfide gas such as a process liquid after sulfidation in a hydrometallurgical treatment of nickel oxide ore. An object of the present invention is to provide a processing method and a processing apparatus for a poor solution capable of effectively reducing dissolved hydrogen sulfide gas.

  Other objects of the present invention and specific advantages obtained by the present invention will become more apparent from the description of embodiments described below.

  In the present invention, an annular aeration tube having a large number of outlets is provided at the bottom of a vertical cylindrical reaction vessel, and the annular aeration tube is stirred while the poor liquid containing hydrogen sulfide is stirred in the reaction vessel. Hydrogen sulfide is removed from the poor liquid by aeration using a simple aeration apparatus that blows aeration gas from a large number of outlets.

That is, the present invention is a method for treating a poor liquid containing hydrogen sulfide, which is provided in a vertical cylindrical reaction vessel, a stirring blade provided in the reaction vessel, and a bottom portion in the reaction vessel. In an aeration tank provided with an annular aeration pipe having a large number of outlets, Fe ³⁺ of a poor liquid containing hydrogen sulfide obtained as a process liquid after sulfiding treatment in a hydrometallurgy plant of nickel oxide ore A part of the reducing agent that is reduced by the reducing power is added, and while agitating by rotation of the stirring blade, aeration gas is introduced into the reaction vessel from a number of outlets of the aeration tube and aerated, The hydrogen sulfide is removed from the poor solution in the hydrogen sulfide removal step provided in the previous stage of the detoxification step.

In the present invention, the reducing agent is reduced by the reducing force of the Fe ³⁺ may be a slurry after leaching containing Fe ^3+.

The present invention is also a treatment apparatus for a poor liquid containing hydrogen sulfide, which is provided at a vertical cylindrical reaction vessel, a stirring blade provided in the reaction vessel, and a bottom portion in the reaction vessel. It consists of an aeration tank equipped with an annular aeration pipe having a large number of outlets and a baffle plate, and hydrogen sulfide obtained as a process liquid after sulfidation treatment in a nickel oxide ore hydrometallurgical plant in the aeration tank A part of the reducing agent that is reduced by the reducing power of Fe ³⁺ is added to the poor solution that is contained, and while agitating by the rotation of the stirring blade, the reaction vessel is used for aeration from the numerous outlets of the aeration tube. Gas is introduced and aerated, and the flow of the gas is rectified by the baffle plate, so that hydrogen sulfide is removed from the poor solution in the hydrogen sulfide removal step provided before the detoxification step. It is characterized by leaving.

  In the present invention, three baffle plates may be provided.

  According to the present invention, an annular aeration pipe having a large number of outlets is provided at the bottom of a vertical cylindrical reaction vessel, and an annular aeration is carried out while stirring a poor liquid containing hydrogen sulfide in the reaction vessel. By effectively aeration using a simple aeration apparatus that blows aeration gas from a large number of outlets of the pipe, hydrogen sulfide can be efficiently aerated and removed from the poor solution.

  In the present invention, in particular, a reaction vessel with a stirring blade for adding slurry after leaching into a poor solution obtained from a sulfidation process of a nickel oxide ore wet processing plant can be suitably used as an aeration tank. It is possible to effectively reduce the hydrogen sulfide gas generated in the recycling process and the subsequent wastewater treatment process.

It is the perspective view which showed through and showed the principal part structure of the structural example of the poor liquid processing apparatus to which this invention is applied. It is process drawing of the hydrometallurgical plant of nickel oxide ore in which a poor liquid processing apparatus is used. It is a perspective view which shows the structural example of the blower outlet provided in the aeration pipe | tube in a poor liquid processing apparatus. It is process drawing of the nickel oxide ore plant by a high pressure acid leaching method.

  Hereinafter, specific embodiments to which the present invention is applied will be described in detail with reference to the drawings.

  The poor liquid treatment method according to the present embodiment is implemented by a poor liquid treatment apparatus 100 having a configuration as shown in FIG. 1, for example.

  This poor liquid treatment apparatus 100 is a circle having a vertical cylindrical reaction vessel 110, a stirring blade 120 provided in the reaction vessel 110, and a large number of air outlets 131 provided at the bottom of the reaction vessel 110. An aeration tank including an annular aeration tube 130. Note that three baffle plates 151 are disposed in the vertical cylindrical reaction vessel 110.

  In the poor liquid treatment method according to the present embodiment, the multiple liquid outlets 131 of the aeration pipe 130 are stirred in the vertical cylindrical reaction vessel 110 while the poor liquid containing hydrogen sulfide is stirred by the rotation of the stirring blade 120. Then, aeration gas is introduced into the reaction vessel 110 and aerated to remove hydrogen sulfide from the poor solution.

  For example, in a hydrometallurgy plant for nickel oxide ore, in the detoxification process as described above, the heavy metal is solidified and removed as a hydroxide by the final neutralization treatment, thereby removing the leach residue generated in the solid-liquid separation process. The nickel poor solution generated in the sulfurization process is made harmless and discarded. At this time, in this embodiment, for example, as shown in the process diagram of FIG. 2, a hydrogen sulfide removal process is provided before the detoxification process, and in the hydrogen sulfide removal process, the above-described poor liquid treatment apparatus 100 is used. Then, hydrogen sulfide is removed from the poor liquid obtained as a process liquid after sulfidation (liquid after sulfidation).

  That is, an annular aeration pipe 130 having a large number of air outlets 131 is provided in a reaction tank for removing hydrogen sulfide from a poor liquid containing hydrogen sulfide obtained as a process liquid after sulfidation in the previous stage of the detoxification process. By providing, this reaction tank is used as the above-mentioned poor liquid processing apparatus 100.

  Specifically, in the poor liquid treatment apparatus 100 as the reaction tank, a poor liquid containing hydrogen sulfide obtained as a process liquid after the sulfidation treatment is charged into the vertical cylindrical reaction vessel 110, and the reaction vessel In 110, the poor liquid containing hydrogen sulfide is stirred by the rotation of the stirring blade 120. Then, in the reaction vessel 110, air as aeration gas is introduced into the poor liquid from the numerous outlets 131 of the aeration pipe 130 and aerated, whereby the sulfur content of the residual hydrogen sulfide in the poor liquid is reduced. It is reduced to sulfur and hydrogen sulfide is removed from the poor solution.

Further, in this nickel oxide ore hydrometallurgical plant, a part of the leached slurry obtained from the leaching process is added to the poor liquid containing hydrogen sulfide obtained as the process liquid after the sulfidation treatment. For this reason, in this hydrogen sulfide removal step, the sulfur content of some residual hydrogen sulfide in the poor liquid is reduced to sulfur by the reducing power of Fe ³⁺ contained in the added slurry. In addition, hydrogen sulfide can be removed from the poor solution.

  That is, the poor liquid treatment apparatus 100 that performs the poor liquid treatment method according to the present embodiment includes a vertical cylindrical reaction vessel 110, a stirring blade 120 provided in the reaction vessel 110, and the reaction vessel 110. And an aeration tank provided with an annular aeration pipe 130 having a large number of air outlets 131 provided at the bottom of the tank, while stirring the poor liquid containing hydrogen sulfide by the rotation of the stirring blade 120 in the aeration tank, Aeration gas is introduced into the reaction vessel 110 from the numerous outlets 131 of the aeration pipe 130 and aerated to remove hydrogen sulfide from the poor solution.

  As described above, in the poor liquid treatment apparatus 100, not only the poor liquid containing hydrogen sulfide is uniformly stirred by the rotation of the stirring blade 120 in the reaction vessel 110, that is, the aeration tank, but also the aeration gas is supplied to the reaction vessel 110. Infuse. As a result, residual hydrogen sulfide is expelled from the stirred poor liquid by aeration, and the residual concentration of hydrogen sulfide is reduced.

  Moreover, in this poor liquid treatment apparatus 100, aeration is performed via an annular aeration tube 130 having a large number of air outlets 131 provided at the bottom of the reaction vessel 110, and bubbles flowing into the reaction vessel 110 are removed. The total area of the bubbles is increased by breaking them down. Thereby, many bubbles can be contacted with the poor liquid containing hydrogen sulfide uniformly stirred in the reaction vessel 110, and a high aeration effect can be obtained. That is, since the gas for aeration supplied into the reaction vessel 110 is dispersed on the bottom of the aeration tank immediately after being supplied, it can be efficiently aerated over the entire poor solution.

  Usually, the set time of the reaction in the stirring reaction apparatus is generally shorter than a sufficient aeration time by a general aeration apparatus. However, according to the poor liquid treatment apparatus 100, since the residence time in the reaction vessel 110 is assumed by providing the reaction vessel 110 with an aeration function, it is not always necessary to ensure a sufficient aeration time. As described above, aeration can be performed efficiently and hydrogen sulfide can be effectively reduced.

  The poor liquid from which hydrogen sulfide has been removed by the poor liquid treatment apparatus 100 can be returned to the solid-liquid separation process and reused as washing water, as shown in the process diagram of FIG.

  As described above, the hydrogen sulfide removing step is provided before the detoxification step, and in this hydrogen sulfide removing step, the residual hydrogen sulfide can be effectively reduced by aeration using the above-described poor liquid treatment apparatus 100. Therefore, generation of hydrogen sulfide gas in the process of reusing the solution after sulfidation or the wastewater treatment process can be suppressed.

  The gas for aeration is not particularly limited as long as it is a gas that maintains bubbles in the liquid, that is, does not easily dissolve in the liquid, but it is preferable in terms of cost to use air.

  The shape of the aeration tube is not particularly limited, but it is preferably formed in an annular shape having a size of 70 to 90% with respect to the diameter of the reaction vessel 110.

  Here, regarding the shape of the aeration tube 130, in Table 1, the relationship between the diameter of the aeration tube 130 and the aeration effect when the diameter of the aeration tube 130 is changed with respect to the diameter of the reaction vessel 110 is observed. The results are shown.

  As is apparent from the observation results shown in Table 1, the aeration pipe 130 in the poor liquid treatment apparatus 100 is formed in an annular shape having a size of 70 to 90% with respect to the diameter of the reaction vessel 110. It can be seen that a high aeration effect can be obtained.

  In order to stabilize the flow in the reaction vessel 110 of the poor liquid treatment apparatus 100, it is necessary to raise the air along the tank wall. In this respect, by forming the aeration pipe 130 in the poor liquid treatment apparatus 100 into an annular shape having a size of 70 to 90% of the diameter of the reaction vessel 110, the air can be efficiently raised along the tank wall. .

  Moreover, although the air blower outlet 131 formed in an aeration pipe | tube is not specifically limited, It is preferable to form in the circle whose diameter is 10-20 mm.

  Here, regarding the air outlet 131 formed in the aeration pipe, Table 2, the relationship between the diameter of the air outlet 131 and the aeration effect in the case where the air outlet 131 is circular and the diameter is changed. The observation result is shown.

  As is apparent from the observation results shown in Table 2, the air outlet 131 of the aeration pipe 130 in the poor liquid treatment apparatus 100 is formed in a circular shape having a diameter of 10 to 20 mm, thereby obtaining a high aeration effect. I understand that I can do it.

  It is presumed that there is an optimum bubble size in the density and flow characteristics of the poor solution, and if it is less than 10 mm, the bubble rising speed in the poor solution is too slow, while if it is larger than 20 mm, it is considered that it becomes too fast. .

  The number of the air outlets 131 is not particularly limited, and is preferably determined as appropriate depending on the circumferential length of the aeration pipe. For example, the number is preferably about 10, more preferably 20. More preferred.

  Here, regarding the number of air outlets 131, Table 3 shows the results of observing the relationship between the number of air outlets 131 and the aeration effect when the number of air outlets 131 is changed.

  As is apparent from the observation results shown in Table 3, by setting the number of air outlets 131 of the aeration pipe 130 in the poor liquid treatment apparatus 100 to ten, a high aeration effect can be obtained. It can be seen that an even higher aeration effect can be obtained.

  In the aeration pipe 130, increasing the number of air outlets 131 weakens the upward flow of air and increases the residence time of air in the aeration tank, so that aeration efficiency increases. If the number of the air outlets 131 is less than 10, the aeration effect becomes insufficient. If the number is increased successively, the effect increases, but if the number is more than 20, the aeration effect is hardly improved further.

  Further, the air outlet 131 is not a mere hole, but a short pipe (blower) attached to the provided hole is preferable because the gas flow is rectified and the bubble size is stabilized. Moreover, it is preferable that the number of the blower outlets shall be about 10-20 pieces.

  That is, for example, as shown in FIG. 3, the aeration pipe 130 obtains an even higher aeration effect by performing aeration with about 10 to 20 short pipes 131 </ b> A installed at equal intervals as the air outlet 131. be able to.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

  In this example, in the hydrogen sulfide removal step provided before the detoxification step in the hydrometallurgical plant on nickel oxide ore, the poor liquid treatment using the poor liquid treatment apparatus 100 described above was performed.

  Table 4 shows the results obtained by measuring the dissolved hydrogen sulfide concentration in the poor solution with and without aeration.

  As is apparent from the measurement results shown in Table 4, when aeration is not performed, the dissolved hydrogen sulfide concentration is 20 ppm at the inlet of the aeration tank and 15 ppm at the outlet, whereas when aeration is performed, the concentration at the outlet of the aeration tank is The concentration of hydrogen sulfide was significantly reduced to 5 ppm, and dissolved hydrogen sulfide in the poor liquid could be effectively reduced by aeration. Thus, it was found that by treating the poor liquid using the poor liquid treatment apparatus 100, the dissolved hydrogen sulfide concentration in the poor liquid can be effectively reduced by the action of the aeration.

  100,200 Heavy metal removal device, 110 reaction vessel, 120 stirring blade, 130 aeration pipe, 131 air outlet, 131A short pipe, 151 baffle plate

That is, the present invention is a method for treating a poor liquid containing hydrogen sulfide, which is provided in a vertical cylindrical reaction vessel, a stirring blade provided in the reaction vessel, and a bottom portion in the reaction vessel. many in the aeration tank and a aeration tube annular with outlet for barren solution containing hydrogen sulfide obtained as process solution after sulfurization process in hydrometallurgy plant nickel oxide ore, the Fe ³⁺ A part of the leached slurry containing was added, aerated by introducing aeration gas into the reaction vessel from a number of outlets of the aeration tube while stirring by rotation of the stirring blade , By rectifying the flow, hydrogen sulfide is removed from the poor solution in the hydrogen sulfide removal step provided in the preceding stage of the detoxification step.

The present invention is also a treatment apparatus for a poor liquid containing hydrogen sulfide, which is provided at a vertical cylindrical reaction vessel, a stirring blade provided in the reaction vessel, and a bottom portion in the reaction vessel. It consists of an aeration tank equipped with an annular aeration pipe having a large number of outlets and a baffle plate, and hydrogen sulfide obtained as a process liquid after sulfidation treatment in a nickel oxide ore hydrometallurgical plant in the aeration tank A part of the leached slurry containing Fe ³⁺ is added to the poor liquid, and the aeration gas is introduced into the reaction vessel from the numerous outlets of the aeration pipe while stirring by the rotation of the stirring blade. The gas flow is rectified by the baffle plate to remove hydrogen sulfide from the poor liquid in the hydrogen sulfide removal step provided before the detoxification step. It is characterized by that.

Claims (4)

In an aeration tank comprising a vertical cylindrical reaction vessel, an agitating blade provided in the reaction vessel, and an annular aeration tube having a number of outlets provided at the bottom of the reaction vessel,
A part of the reducing agent that is reduced by the reducing power of Fe ³⁺ is added to the poor liquid containing hydrogen sulfide obtained as the process liquid after the sulfidation treatment in the nickel oxide ore hydrometallurgical plant. While agitating, aeration gas is introduced into the reaction vessel from a large number of outlets of the aeration tube and aerated, so that hydrogen sulfide is removed from the poor solution in the hydrogen sulfide removal step provided in the previous stage of the detoxification step. A method for treating a poor solution containing hydrogen sulfide, characterized by removing water. Reducing agent for reducing the reducing power of the Fe ^3+, the processing method of the barren solution containing hydrogen sulfide according to claim 1, characterized in that the slurry after leaching containing Fe ^3+. Aeration comprising a vertical cylindrical reaction vessel, an agitating blade provided in the reaction vessel, an annular aeration tube having a number of outlets provided at the bottom of the reaction vessel, and a baffle plate A tank,
In the aeration tank, with respect to the poor liquid containing hydrogen sulfide obtained as a process liquid after the sulfidation treatment in the nickel oxide ore hydrometallurgical plant, a part of the reducing agent that is reduced by the reducing power of Fe ³⁺ is added, While agitating by the rotation of the stirring blade, aeration gas is introduced into the reaction vessel from a number of outlets of the aeration pipe and aerated, and the flow of the gas is rectified by the baffle plate. An apparatus for treating a poor solution containing hydrogen sulfide, wherein hydrogen sulfide is removed from the poor solution in a hydrogen sulfide removal step provided in a preceding stage of the detoxification step.   The apparatus for treating a poor solution containing hydrogen sulfide according to claim 3, wherein three baffle plates are provided.