WO2018092694A1 - マンガンの除去方法 - Google Patents
マンガンの除去方法 Download PDFInfo
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- WO2018092694A1 WO2018092694A1 PCT/JP2017/040634 JP2017040634W WO2018092694A1 WO 2018092694 A1 WO2018092694 A1 WO 2018092694A1 JP 2017040634 W JP2017040634 W JP 2017040634W WO 2018092694 A1 WO2018092694 A1 WO 2018092694A1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
- C02F1/64—Heavy metal compounds of iron or manganese
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
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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
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- C22B47/00—Obtaining manganese
Definitions
- the present invention relates to a method for removing manganese, and more particularly, to a method for efficiently removing manganese from wastewater (post-sulfurization liquid) generated in a hydrometallurgical process of nickel oxide ore.
- HPAL process In a process (HPAL process) in which an acid such as sulfuric acid is added to nickel oxide ore under high temperature and pressure to leach valuable components such as nickel, and then impurities are separated from the obtained leachate to recover nickel.
- impurities such as iron, aluminum, manganese, magnesium and calcium contained in the raw material nickel oxide ore are present.
- the components that need to be removed by wastewater treatment generally include iron (floating particles whose main component is iron oxide), aluminum, and manganese.
- iron can be completely settled and removed by subjecting suspended particles to sedimentation with a thickener or the like, and discharging and passing the obtained supernatant liquid to a tailing dam or the like.
- the pH is adjusted to 9 or more by adding an alkali, or a starch in the form of manganese dioxide is formed by adding an oxidizing agent. Need to be removed.
- the amount of generated wastewater becomes large and the treatment is performed in a reducing atmosphere. Therefore, for example, when manganese is removed by oxidation, if it is oxidized by an oxidizing agent such as sodium hypochlorite or ozone, a large cost is required, which is not realistic.
- an oxidizing agent such as sodium hypochlorite or ozone
- manganese is precipitated and removed in the form of manganese hydroxide by adjusting the pH of the waste water to 9 or more.
- alkali which is a neutralizing agent
- magnesium contained in a large amount in the wastewater first becomes a hydroxide, and the alkali is consumed for the hydroxide formation of magnesium. Therefore, it becomes necessary to add an alkali in excess of the amount of manganese, which is a cause of cost.
- Patent Document 1 discloses a method of preferentially removing manganese from an acidic manganese-containing solution containing magnesium by an oxidation neutralization method. Specifically, when removing manganese as a precipitate from an acidic manganese-containing solution, the pH of the manganese-containing acidic solution containing magnesium is set to 8.2 to 8.8, and the oxidation-reduction potential (mV) of the solution is set. ) Is adjusted with air, oxygen, ozone or peroxide so that it becomes 10 mV to 500 mV, and a method of precipitating and removing manganese preferentially is disclosed.
- mV oxidation-reduction potential
- Non-Patent Documents 1 to 5 disclose bacteria such as Bacillus genus, Hyphomicrobium genus, Magnetospirillum genus, Pseudomonas genus and Geobacter genus as bacteria that oxidize manganese.
- bacteria such as Bacillus genus, Hyphomicrobium genus, Magnetospirillum genus, Pseudomonas genus and Geobacter genus as bacteria that oxidize manganese.
- the present invention has been proposed in view of the above-described circumstances, and manganese contained in wastewater generated through the HPAL process is effectively reduced in the amount of a chemical such as a neutralizing agent. It aims at providing the removal method of manganese which can be removed efficiently, without using cost and an installation.
- the present inventor has intensively studied to solve the above-described problems. As a result, the sludge generated in the piping used to discharge the wastewater is added to the wastewater and mixed with stirring, without increasing the amount of chemicals such as neutralizers used conventionally. The present inventors have found that manganese can be removed efficiently and have completed the present invention.
- a sulfiding agent is added to a leachate produced by acid leaching of nickel oxide ore containing at least nickel and manganese to add a sulfide containing nickel and a post-sulfurization solution.
- a second invention of the present invention is the method for removing manganese according to the first invention, wherein the pipe is a drainage pipe in which manganese oxidizing bacteria are present, and the sludge contains the manganese oxidizing bacteria. It is.
- the third invention of the present invention is the first or second invention, wherein in the neutralization treatment for the post-sulfurization solution, the pH is in the range of 8.0 or more and less than 9.0 by adding the alkali. This is a method for removing manganese.
- a fourth invention of the present invention is a method for removing manganese according to any one of the first to third inventions, wherein the sludge is added to the post-neutralized solution and contacted for 4 hours or more.
- the amount of the sludge added to the post-neutralization solution is the post-neutralization solution obtained after the neutralization treatment. This is a method for removing manganese that is 50 to 500 times the amount of manganese contained.
- the sixth aspect of the present invention is the removal of manganese according to any one of the first to fifth aspects, wherein the neutralized solution and the sludge are stirred and mixed at a temperature of 35 ° C. or higher and 60 ° C. or lower. Is the method.
- manganese contained in waste water generated through the HPAL process can be efficiently removed while effectively reducing the amount of a chemical such as a neutralizing agent.
- the present embodiment a specific embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- this invention is not limited to the following embodiment, A various change is possible in the range which does not change the summary of this invention.
- the method for removing manganese is a method for removing manganese from wastewater containing manganese.
- the waste water is a hydrometallurgical process (hereinafter referred to as “HPAL process”) in which nickel oxide ore containing at least nickel and manganese is added with an acid such as sulfuric acid and subjected to leaching treatment under high temperature and high pressure to recover nickel.
- HPAL process hydrometallurgical process
- nickel oxide ore containing at least nickel and manganese is added with an acid such as sulfuric acid and subjected to leaching treatment under high temperature and high pressure to recover nickel.
- the sulfidized liquid is discharged after the nickel is separated and recovered by sulfidation.
- the manganese removal method according to the present embodiment is a manganese removal method for removing manganese from the post-sulfurization solution after separating nickel in the HPAL process as described above.
- a slurry of nickel oxide ore containing at least nickel and manganese is subjected to a leaching treatment to generate a leachate, and then hydrogen sulfide gas or the like is added to the leachate.
- nickel is recovered as a sulfide.
- the leachate can be appropriately neutralized (first neutralization) to separate and remove impurities, and the resulting neutralized solution can be sulfurized.
- the post-sulfurization solution obtained after separating and recovering the nickel sulfide contains manganese and other impurity components such as magnesium and aluminum. Remove ingredients.
- this neutralization process with respect to the liquid after sulfidation is a so-called waste water treatment and is a final neutralization treatment before waste water, it is also referred to as a final neutralization treatment.
- the post-sulfurization solution is a solution obtained by adding a sulfiding agent and performing a sulfidation treatment, so that it is a relatively highly reducible solution. Therefore, when an oxidizing agent is added and manganese is separated and removed as a starch in the form of manganese dioxide as in the prior art, the amount of oxidizing agent used for the oxidation increases and the processing cost increases.
- the solution after sulfidation often contains magnesium as well as manganese, and the alkali is preferentially used for the hydroxide formation of magnesium only by neutralizing the pH with a neutralizing agent such as an alkali. In order to finally separate and remove the entire amount of manganese, a large amount of neutralizing agent is required.
- manganese can be separated only by pH adjustment based on neutralization by adding alkali to the post-sulfurization solution to be treated.
- the manganese content is reduced to some extent by removing the slag, and then a specific sludge is added to the post-sulfurization solution to perform a stirring process.
- manganese can be efficiently separated and removed from the post-sulfurization solution, which is waste water, while effectively reducing the amount of a chemical such as a neutralizing agent.
- PH adjustment step In the method for removing manganese according to the present embodiment, an alkali is added to the post-sulfurization solution to be treated to neutralize it, and the pH of the solution is adjusted to neutralize the starch and the post-neutralization solution. Process to generate. This process is referred to as “pH adjustment process”.
- the pH adjustment step by adjusting the pH by adding alkali to the post-sulfurization solution containing manganese, manganese that can be separated only by the pH adjustment is roughly separated and removed, and the post-sulfurization solution Reduce the manganese content.
- impurity components such as magnesium contained together with manganese in the sulfidized solution can be separated and removed.
- the pH of the solution is preferably adjusted to a range of 8.0 or more and less than 9.0 by adding an alkali to the sulfidized solution.
- This pH adjustment step does not neutralize the manganese contained in the solution after sulfidation to a range exceeding pH 9.2 where it can be completely separated practically, but dares to leave a small amount of manganese in the wastewater at a pH of 8.0 to 9.0.
- Adjustment control is preferably performed in a range of less than about. If it is such a pH range, it can control easily by adding a small amount of neutralizing agents, and can also remove manganese moderately.
- alkali neutralizing agent
- Slurries such as slaked lime and limestone
- the pH adjustment range preferably in the range of 8.0 or more and less than 9.0, the use amount of the neutralizing agent can be effectively reduced as compared with the prior art, Efficient processing can be performed.
- a specific sludge is added to and mixed with the post-neutralization solution obtained by the neutralization treatment, and a stirring treatment is performed.
- the post-neutralization solution to which sludge is added is a solution after separating and removing the neutralized starch produced by the neutralization treatment. This process is referred to as a “sludge mixing process”.
- the sludge generated in the pipe for discharging the neutralized liquid after wastewater treatment is added to the post-neutralized liquid stored in a predetermined reaction vessel, and batch operation is performed. It is characterized by stirring and mixing.
- the pipe for discharging the liquid after neutralization is a drain pipe for discharging after the waste water treatment, and has manganese oxide bacteria on the pipe surface, for example, having a length of 3 km or more. After draining the post-sulfurized solution obtained through the HPLA process, manganese oxide bacteria are present on the surface of the drain pipe for discharging the treated solution as a water channel deposit.
- sludge generated in the pipe for discharging the liquid after neutralization refers to sludge containing manganese oxidizing bacteria.
- the manganese which remains in the post-neutralization liquid is manganese. It is precipitated by the oxidizing action of oxidizing bacteria and separated and removed.
- Manganese-oxidizing bacteria is a general term for microorganisms that have the ability to oxidize manganese.
- the manganese-oxidizing bacterium is not particularly limited, and examples thereof include the genus Hyphomicrobium, the genus Magnetospirillum, the genus Geobacter, the genus Bacillus, and the genus Pseudomonas.
- Wastewater such as post-sulfurization liquid discharged through the HPAL process contains various salts. By passing such wastewater through the drainage pipe, manganese oxide bacteria are contained in the drainage pipe. The environment can grow well.
- such drainage pipes further contain essential nutrients and the like for the manganese oxidizing bacteria so that the manganese oxidizing bacteria can efficiently grow.
- the existence ratio (concentration) of manganese-oxidizing bacteria in the drain pipe is preferably a high concentration of about 100 mg / L to 1000 mg / L, for example.
- the drainage pipe is passed through.
- the manganese concentration in the wastewater supplied to the drainage pipe is increased by approximately 1 mg / L per month, and manganese oxidizing bacteria present in the drainage pipe In contrast, it is preferable to gradually apply a manganese load.
- the manganese oxidation bacteria in a drainage channel can be efficiently propagated, and the film
- manganese oxidizing bacteria collected from the drainage pipe of the wastewater treatment facility of the smelter operating on Palawan Island in the Philippines were cultured and subjected to the test.
- the manganese-oxidizing bacteria that can be used are not limited to such specific production areas.
- the method of adding sludge to the neutralized solution is not particularly limited. For example, after a predetermined amount of neutralized solution is charged into a predetermined reaction vessel as described above, a slurry of sludge having a predetermined concentration is added thereto. Add and add.
- the amount of sludge added is determined by the concentration of manganese remaining in the solution after neutralization, but it is preferable to add approximately 50 to 500 times the amount of manganese contained in the solution after neutralization before sludge addition. More preferably, an amount of 80 to 200 times is added, and an amount of 100 times is particularly preferable.
- the amount 50 to 500 times the amount of manganese in the post-neutralization solution mentioned here means that, for example, when the concentration of manganese contained in the post-neutralization solution is 1 g / L, the concentration is 50 g / L. It means adding a slurry of sludge that is L-500 g / L.
- the amount of sludge added is more than 500 times the amount of manganese, the removal effect of manganese will not be further improved, but a large amount of sludge will be required, ensuring sludge and labor, etc. It is not preferable in terms of cost and efficiency.
- the amount of sludge added is less than 50 times the amount of manganese, the amount of manganese removed by the sludge may be very small, and manganese may not be sufficiently removed.
- stirring and mixing are performed by batch operation.
- the manganese concentration in the post-neutralization liquid containing manganese gradually decreases by stirring and mixing with sludge, but generally the rate at which the manganese concentration decreases decreases with the lapse of treatment time. If the contact time between the neutralized solution and the sludge is extended, the manganese concentration in the neutralized solution decreases, that is, the amount of manganese removal increases. However, if the contact time exceeds 10 hours, the effect is increased. Is limited. Therefore, the upper limit of the processing time is preferably 10 hours or less.
- FIG. 1 is a graph showing the transition of the manganese concentration in the neutralized solution with respect to the time since the sludge containing manganese-oxidizing bacteria was added to the neutralized solution, that is, the treatment time. Test conditions and the like will be described in Example 1. As shown in FIG. 1, in the initial stage where the sludge is added and mixed, the manganese concentration in the neutralized final solution decreases rapidly, but the rate of decrease in manganese concentration gradually increases as the treatment time elapses. It turns out that it becomes loose.
- a predetermined amount of sludge is added to the solution after neutralization and contacted for a certain period of time, then the treatment with the sludge is terminated and new sludge is added. Is preferable, and more efficient processing is possible.
- reaction time is a time for adding sludge to contact the post-neutralization liquid.
- the contact time is particularly preferably 4 to 6 hours.
- room temperature room temperature
- the reaction efficiency can be increased, and the manganese removal efficiency in a short time increases. More preferably, the temperature condition is 40 ° C. or higher and 55 ° C. or lower.
- the sludge contains manganese oxidizing bacteria.
- Manganese-oxidizing bacteria are one of the common types of bacteria, so if they are reacted at a high liquid temperature, for example, above 60 ° C, the proteins that make up the bacteria will change and suppress growth and reaction efficiency. There is a possibility that. Therefore, the liquid temperature during the reaction is preferably 60 ° C. or less, and more preferably 55 ° C. or less.
- a method for adjusting the liquid temperature of the liquid after neutralization for example, a method of heating using a fossil fuel and a heat exchanger, a method of heating by operating a heat exchanger with electric power or other power, and utilizing solar heat
- Various methods such as a method of using a geothermal heat or other factory heat source, a method of using a biological fermentation heat source, or the like can be used.
- the method for adjusting the liquid temperature is not particularly limited as long as a heat source for raising the temperature and maintaining the temperature can be secured.
- the neutralized solution that passes through the drainage pipe flows toward the outlet through which the drainage pipe is discharged into the sea area, etc., but as described above, the surface of the inner wall of the drainage pipe has manganese oxide bacteria. As a result, the manganese is completely removed to a concentration of 1 mg / L or less by passing through the drainage pipe.
- the residence time of the neutralized solution when passing through the drain pipe corresponds to the reaction time of the treatment in the pipe, the residence time in the drain pipe is obtained from the required reaction time. What is necessary is just to determine the length of the piping to fill and the inner diameter of the piping.
- the length of the drainage pipe is preferably 3 km or more, and the drainage treatment is preferably performed so as to pass through the drainage pipe having such a length over a residence time of 1 hour or more. .
- Example 1 Verification of manganese removal method> [Example 1] The slurry of nickel oxide ore containing at least nickel and manganese was acid leached with sulfuric acid under high temperature and high pressure, and a hydrometallurgy was performed to recover valuable metals such as nickel by adding a sulfiding agent from the obtained leachate. Thereafter, an operation for removing manganese contained in the drainage source solution was performed using the post-sulfurization solution obtained by the sulfidation treatment as the drainage source solution.
- PH adjustment step First, a slurry of slaked lime is added to the solution after sulfidation, and a neutralization treatment is performed to adjust the pH of the solution to 8.0 to produce a neutralized starch containing magnesium and a small amount of manganese and a solution after neutralization. I let you. Thereafter, the neutralized starch was solid-liquid separated from the neutralized solution. At this time, the manganese concentration contained in the obtained solution after neutralization was 10 mg / L.
- a bacterial base likely to be a manganese-oxidizing bacterium
- the number of sequences is 975
- the number of base sequences of other bacteria is 2,801
- at least 1/4 of the identified DNA is manganese-oxidizing bacteria
- manganese-oxidizing bacteria are present on the inner wall of the pipe. It was confirmed that As manganese-oxidizing bacteria, bacteria of the genus Hyphomicrobium, the genus Magnetospirillum, the genus Geobacter, the genus Bacillus, and the genus Pseudomonas were confirmed.
- the known base sequence means a bacterial base sequence registered in a database at the time of DNA analysis.
- the post-neutralization solution obtained in the pH adjustment step is charged into the reaction vessel, and the prepared sludge for addition is added to the post-neutralization solution at a slurry concentration of 1 g / L
- the slurry was mixed at a normal temperature for 4 hours with mixing.
- FIG. 1 is a graph showing the transition of manganese concentration in the post-neutralization liquid with respect to the processing time (contact time with sludge) in Example 1, and in the post-neutralization liquid by stirring for 4 hours after addition and mixing.
- the manganese concentration decreased to approximately 6 mg / L. Further, when stirring was continued and stirred for 6 hours, the manganese concentration decreased to 5.5 mg / L.
- Example 2 In the same manner as in Example 1, after the sulfurized solution was treated in the pH adjustment step, a sludge slurry having a concentration of 1 g / L was added to the obtained neutralized solution.
- the manganese concentration at the time of stirring and mixing for 3 minutes while stirring at room temperature and the time of stirring and mixing for 0.5 hour were 9.7 mg / L and 8.0 mg / L, respectively. Thereafter, the stirring and mixing time was further extended to 2 hours. As a result, the manganese concentration in the solution after neutralization was 7.3 mg / L.
- Example 2 From the results of Example 2, it was found that an efficient treatment for reducing the amount of neutralizing agent used can be performed. However, based on the results of Example 1, it was found that the contact time (reaction time for stirring and mixing) between the neutralized solution and sludge is preferably 4 hours or longer.
- Example 3 After performing the treatment in the pH adjustment step on the post-sulfurized solution, in Example 3, sludge having a concentration of 0.1 g / L (the amount of manganese contained in the post-neutralized solution) was obtained. Equivalent to 10 times the amount of slurry) was added.
- Example 3 From the results of Example 3, it was found that manganese can be separated and removed by an efficient treatment that reduces the amount of neutralizing agent used. However, compared with the result of Example 1, the manganese reduction effect was small.
- Example 1 In the same manner as in Example 1, the pH adjustment step was performed on the post-sulfurization solution obtained by the hydrometallurgical treatment of nickel oxide ore, and slaked lime slurry was added to the obtained post-neutralization solution. Then, a treatment for increasing the pH from 8.0 to 8.6 was performed.
- the manganese concentration in the obtained treated solution was reduced to 6 mg / L or less.
- the processing cost increases by the amount of slaked lime of the added neutralizing agent, and efficient processing cannot be performed.
- Example 4 Verification of temperature conditions for manganese removal>
- the nickel oxide ore was treated by the HPAL process in the same manner as in Example 1 to obtain a post-sulfurized liquid (drainage) having a manganese concentration of 100 mg / L.
- the obtained waste water was put into a container as it was, and sludge containing manganese-oxidizing bacteria was added to the container for reaction.
- the added sludge is sludge that adheres to the inner wall of the drainage pipe for discharging the wastewater to the outlet as in Example 1, and this sludge has a slurry concentration of 10 g / L (included in the wastewater). Added as a slurry having a manganese concentration of 100 g / L per 1 g / L.
- the mixture was stirred and mixed for 4 hours while adjusting and maintaining the temperature of the wastewater at 40 ° C.
- the manganese concentration in the aqueous solution decreased to 40 mg / L.
- Example 5 In the same manner as in Example 4, sludge was added to a wastewater having a manganese concentration of 100 mg / L as a slurry having a slurry concentration of 10 g / L and reacted. At this time, stirring and mixing were performed for 4 hours while adjusting and maintaining the temperature of the waste water at 50 ° C.
- the manganese concentration in the aqueous solution decreased to 20 mg / L.
- the manganese concentration in the aqueous solution decreased only to about 55 mg / L, and the reaction efficiency was lower than that of Example 4 and Example 5 which were contacted with sludge under relatively high temperature conditions.
- the manganese concentration in the aqueous solution decreased only to about 50 mg / L, and the reaction efficiency was lowered as compared with Examples 4 and 5 which were contacted with sludge under relatively high temperature conditions.
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Abstract
Description
本実施の形態に係るマンガンの除去方法では、処理対象の硫化後液に対してアルカリを添加して中和処理を施し、溶液のpHを調整して中和澱物と中和後液とを生成させる処理を行う。なお、この工程を「pH調整工程」と称する。
次に、本実施の形態に係るマンガンの除去方法では、中和処理により得られた中和後液に対して、特定のスラッジを添加して混合し、撹拌処理を施す。なお、スラッジを添加する中和後液は、中和処理により生成した中和澱物を分離除去した後の溶液である。また、この工程を「スラッジ混合工程」と称する。
具体的に、スラッジ混合工程では、所定の反応容器に収容した中和後液に対して、排水処理後の中和後液を排出するための配管内に生成したスラッジを添加し、バッチ操作で撹拌混合することを特徴としている。
本実施の形態においては、上述したように、所定の反応溶液に収容した中和後液に対して、中和後液を排出するための配管に生成したスラッジ、すなわちマンガン酸化細菌が含まれるスラッジを添加し、撹拌混合する。
上述したように、反応容器内で中和後液にスラッジを添加してマンガンを分離除去したのち、その処理後の中和後液を、排水路配管内に通過させて排水(放流)する。具体的には、スラッジと接触させることによって中和後液中のマンガン濃度が6mg/L以下となる処理したのち、その処理後の中和後液を、排水路配管を介して放流する。
[実施例1]
少なくともニッケルとマンガンとを含有するニッケル酸化鉱石のスラリーを高温高圧下で硫酸により酸浸出し、得られた浸出液から硫化剤を添加してニッケル等の有価金属を回収する湿式製錬を行った。その後、硫化処理により得られた硫化後液を排水元液として用いて、その排水元液に含まれるマンガンを除去する操作を行った。
先ず、硫化後液に消石灰のスラリーを添加して、溶液のpHを8.0に調整する中和処理を施し、マグネシウムや微量のマンガン等を含む中和澱物と中和後液とを生成させた。その後、その中和後液から中和澱物を固液分離した。このとき、得られた中和後液に含まれるマンガン濃度は10mg/Lであった。
次に、中和後液を放流口まで排出するための排水路配管の内壁に付着生成しているスラッジを剥ぎ取って回収し、そのスラッジを添加用のスラッジとして調製した。なお、このスラッジにはマンガン酸化細菌が存在していることが確認された。
上述した処理により、マンガン濃度が6mg/Lまで低下した中和後液を、長さ10kmの排水路配管を通して放流口まで流した。その結果、放流口付近での中和後液に含まれマンガン濃度を測定したところ、1mg/L未満にまで低減されていた。
実施例1と同様に、硫化後液に対してpH調整工程での処理を行ったのち、得られた中和後液に対して濃度1g/Lのスラッジのスラリーを添加した。
硫化後液に対してpH調整工程での処理を行ったのち、実施例3では、得られた中和後液に対して濃度0.1g/Lのスラッジ(中和後液に含まれるマンガン量の10倍の量に相当)のスラリーを添加した。
実施例1と同様に、ニッケル酸化鉱石の湿式製錬処理で得られた硫化後液に対してpH調整工程を実施し、得られた中和後液に対して、消石灰スラリーを追加して添加し続け、pHを8.0から8.6まで上昇させる処理を行った。
[実施例4]
実施例1と同様にしてニッケル酸化鉱石をHPALプロセスで処理して、マンガン濃度が100mg/Lの硫化後液(排水)を得た。マンガン酸化細菌を含むスラッジとの反応に際しての温度条件について検証するために、得られた排水をそのまま容器に入れ、この容器にマンガン酸化細菌を含むスラッジを添加して反応させた。なお、添加したスラッジは、実施例1と同様に排水を放流口まで排出するための排水路配管の内壁に付着生成しているスラッジであり、このスラッジを10g/Lのスラリー濃度(排水に含まれるマンガン濃度1g/Lあたり100g/Lに相当する濃度)のスラリーとして添加した。
実施例4と同様に、マンガン濃度100mg/Lの排水に、スラッジを10g/Lのスラリー濃度のスラリーとして添加して反応させた。このとき、排水の液温を50℃に調整し維持しながら4時間の撹拌混合を行った。
実施例4と同様に、マンガン濃度100mg/Lの排水に、スラッジを10g/Lのスラリー濃度のスラリーとして添加して反応させた。このとき、排水の液温を5℃に調整し維持しながら4時間の撹拌混合を行った。
実施例4と同様に、マンガン濃度100mg/Lの排水に、スラッジを10g/Lのスラリー濃度のスラリーとして添加して反応させた。このとき、排水の液温を20℃に調整し維持しながら4時間の撹拌混合を行った。
Claims (6)
- 少なくともニッケルとマンガンとを含有するニッケル酸化鉱石を酸浸出して生成した浸出液に硫化剤を添加してニッケルを含有する硫化物と硫化後液とを得たのち、該硫化物を分離した硫化後液からマンガンを除去するマンガンの除去方法であって、
前記硫化後液にアルカリを添加して中和処理し、中和澱物と中和後液とを生成させ、
前記中和澱物を分離した中和後液に対して、該中和後液を排出するための配管内に生成しているスラッジを添加して撹拌混合する
マンガンの除去方法。 - 前記配管は、マンガン酸化細菌が存在する排水路配管であり、
前記スラッジは、前記マンガン酸化細菌を含有する
請求項1に記載のマンガンの除去方法。 - 前記硫化後液に対する中和処理では、前記アルカリを添加することによりpHを8.0以上9.0未満の範囲の調整する
請求項1又は2に記載のマンガンの除去方法。 - 前記中和後液に前記スラッジを添加して4時間以上接触させる
請求項1乃至3のいずれか1項に記載のマンガンの除去方法。 - 前記中和後液に対する前記スラッジの添加量が、前記中和処理後に得られた中和後液に含まれるマンガン量の50倍~500倍の量である
請求項1乃至4のいずれか1項に記載のマンガンの除去方法。 - 35℃以上60℃以下の温度で前記中和後液と前記スラッジとを撹拌混合する
請求項1乃至5のいずれか1項に記載のマンガンの除去方法。
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JPH09248576A (ja) * | 1996-03-14 | 1997-09-22 | Taiheiyo Kinzoku Kk | マグネシュウムを含有するマンガン酸性溶液からのマンガンの優先的除去法 |
JP2000245444A (ja) * | 1998-12-28 | 2000-09-12 | Agency Of Ind Science & Technol | 新規微生物の培養方法及びこれを用いた水処理方法 |
JP2009063239A (ja) * | 2007-09-06 | 2009-03-26 | Chubu Electric Power Co Inc | 熱交換器のスケール対策法 |
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JPH09248576A (ja) * | 1996-03-14 | 1997-09-22 | Taiheiyo Kinzoku Kk | マグネシュウムを含有するマンガン酸性溶液からのマンガンの優先的除去法 |
JP2000245444A (ja) * | 1998-12-28 | 2000-09-12 | Agency Of Ind Science & Technol | 新規微生物の培養方法及びこれを用いた水処理方法 |
JP2009063239A (ja) * | 2007-09-06 | 2009-03-26 | Chubu Electric Power Co Inc | 熱交換器のスケール対策法 |
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