JP2022039700A - Method for producing metal hydroxide and apparatus for producing metal hydroxide - Google Patents
Method for producing metal hydroxide and apparatus for producing metal hydroxide Download PDFInfo
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Abstract
Description
本発明は、金属水酸化物の製造方法、および、金属水酸化物の製造装置に関する。 The present invention relates to a method for producing a metal hydroxide and an apparatus for producing a metal hydroxide.
金属を含む溶液から該金属の水酸化物を製造する方法として、金属を含む溶液とアルカリ剤を含む溶液とを混合し、金属とアルカリ剤とを反応させ、金属を水酸化物として不溶化処理する方法（アルカリ沈殿法）が知られている。例えば、特許文献１に開示された方法では、アルカリ剤として水酸化ナトリウムを含む溶液に、金属として亜鉛を含む溶液を添加して混合液を形成し、該混合液を、所定時間、撹拌混合して金属の水酸化物を生成する。 As a method for producing a hydroxide of the metal from a solution containing a metal, a solution containing the metal and a solution containing an alkaline agent are mixed, the metal and the alkaline agent are reacted, and the metal is insolubilized as a hydroxide. A method (alkali precipitation method) is known. For example, in the method disclosed in Patent Document 1, a solution containing sodium hydroxide as an alkaline agent is added to a solution containing zinc as a metal to form a mixed solution, and the mixed solution is stirred and mixed for a predetermined time. To produce metal hydroxides.
このように生成された金属の水酸化物は、混合液中にスラッジとして存在するため、該スラッジを種々の方法で濾過し、濾過したスラッジを種々の方法で脱水処理することで、脱水ケーキとして回収される。 Since the metal hydroxide thus produced exists as sludge in the mixed solution, the sludge is filtered by various methods and the filtered sludge is dehydrated by various methods to obtain a dehydrated cake. It will be collected.
しかしながら、特許文献１に記載されている方法のように、所謂バッチプロセス方式で金属の水酸化物を生成すると、金属の水酸化物の粒子径に、比較的大きなバラつきが生じることになる（粒子径の標準偏差が比較的大きくなる）。このように、粒子径に比較的大きなバラつきが生じると、例えば、金属の水酸化物を含むスラッジ中に比較的多くの水分が包含され、スラッジの体積や質量の低減を図ることが困難になったり、脱水ケーキを回収する作業に多大な手間がかかったりすることがある。 However, when a metal hydroxide is produced by a so-called batch process method as in the method described in Patent Document 1, the particle size of the metal hydroxide has a relatively large variation (particles). The standard deviation of the diameter is relatively large). When the particle size varies relatively large in this way, for example, a relatively large amount of water is contained in the sludge containing the hydroxide of the metal, and it becomes difficult to reduce the volume and mass of the sludge. Or, the work of collecting the dehydrated cake may take a lot of time and effort.
本発明は、このような現状に鑑みてなされたものであり、粒子径のバラつきが比較的小さい金属の水酸化物を製造することができる金属水酸化物の製造方法、および、金属水酸化物の製造装置を提供することを課題とする。 The present invention has been made in view of the present situation, and is a method for producing a metal hydroxide capable of producing a metal hydroxide having a relatively small variation in particle size, and a metal hydroxide. It is an object to provide the manufacturing equipment of.
本発明に係る金属水酸化物の製造方法は、
下記工程（１）を含む。
工程（１）：
マグネシウム、アルミニウム、マンガン、亜鉛、鉄、カドミウム、コバルト、ニッケル、スズ、アンチモン、ビスマス、銅および銀からなる群から選ばれる少なくとも１種の金属Ｍを含む溶液と、水酸化ナトリウム、水酸化カリウムおよび水酸化カルシウムからなる群から選ばれる少なくとも１種のアルカリ剤を含む溶液または懸濁液とを、連続プロセス方式を用いて、反応槽に供給しつつ、滞留時間が１～３０時間の条件で、金属Ｍとアルカリ剤とを反応させて、金属Ｍの水酸化物を得る工程
The method for producing a metal hydroxide according to the present invention is
The following step (1) is included.
Step (1):
A solution containing at least one metal M selected from the group consisting of magnesium, aluminum, manganese, zinc, iron, cadmium, cobalt, nickel, tin, antimony, bismuth, copper and silver, and sodium hydroxide, potassium hydroxide and A solution or suspension containing at least one alkaline agent selected from the group consisting of calcium hydroxide is supplied to the reaction vessel by a continuous process method, and the residence time is 1 to 30 hours. Step of reacting metal M with an alkaline agent to obtain hydroxide of metal M
本発明に係る金属水酸化物の製造装置は、
マグネシウム、アルミニウム、マンガン、亜鉛、鉄、カドミウム、コバルト、ニッケル、スズ、アンチモン、ビスマス、銅および銀からなる群から選ばれる少なくとも１種の金属Ｍを含む溶液を貯蔵する容器Ａと、
水酸化ナトリウム、水酸化カリウムおよび水酸化カルシウムからなる群から選ばれる少なくとも１種のアルカリ剤を含む溶液または懸濁液を貯蔵する容器Ｂと、
容器Ａから金属Ｍを含む溶液が供給され、容器Ｂからアルカリ剤を含む溶液または懸濁液が供給され、金属Ｍとアルカリ剤とを反応させて金属Ｍの水酸化物を生成する反応槽Ｃと、
反応槽Ｃから金属Ｍの水酸化物を含む処理液が供給される処理液槽Ｄと、
を備え、
容器Ａから反応槽Ｃへの溶液の供給、容器Ｂから反応槽Ｃへの溶液または懸濁液の供給、反応槽Ｃから処理液槽Ｄへの処理液の供給は、連続プロセス方式にて実施され、
容器Ａから反応槽Ｃへの溶液の単位時間当たりの供給量と容器Ｂから反応槽Ｃへの溶液または懸濁液の単位時間当たりの供給量とが、反応槽Ｃにおける滞留時間が１～３０時間となるように設定されている。
The apparatus for producing a metal hydroxide according to the present invention is
A container A for storing a solution containing at least one metal M selected from the group consisting of magnesium, aluminum, manganese, zinc, iron, cadmium, cobalt, nickel, tin, antimony, bismuth, copper and silver.
A container B for storing a solution or suspension containing at least one alkaline agent selected from the group consisting of sodium hydroxide, potassium hydroxide and calcium hydroxide.
A reaction tank C in which a solution containing a metal M is supplied from the container A, a solution or a suspension containing an alkaline agent is supplied from the container B, and the metal M and the alkaline agent are reacted to form a hydroxide of the metal M. When,
The treatment liquid tank D to which the treatment liquid containing the hydroxide of the metal M is supplied from the reaction tank C, and
Equipped with
The supply of the solution from the container A to the reaction tank C, the supply of the solution or suspension from the container B to the reaction tank C, and the supply of the treatment liquid from the reaction tank C to the treatment liquid tank D are carried out by a continuous process method. Being done
The supply amount of the solution from the container A to the reaction tank C per unit time and the supply amount of the solution or suspension from the container B to the reaction tank C per unit time are 1 to 30 in the reaction tank C. It is set to be the time.
本発明によれば、粒子径のバラつきが比較的小さい金属の水酸化物を製造することができる金属水酸化物の製造方法、および、金属水酸化物の製造装置を提供することができる。 According to the present invention, it is possible to provide a method for producing a metal hydroxide capable of producing a metal hydroxide having a relatively small variation in particle size, and an apparatus for producing a metal hydroxide.
以下、本発明の実施形態について説明するが、本発明は、以下の実施形態に限定されるものではない。なお、本明細書では、各種の濃度および添加量は、特に断りのない限り、純分換算の質量割合である。 Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present specification, various concentrations and addition amounts are mass ratios in terms of pure content unless otherwise specified.
本実施形態に係る金属水酸化物の製造方法は、金属Ｍを含む溶液と、アルカリ剤を含む溶液または懸濁液（以下では、「アルカリ剤を含む溶液等」とも記す）とを、連続プロセス方式を用いて、反応槽に供給しつつ、金属Ｍとアルカリ剤とを反応させて、金属Ｍの水酸化物を得る工程（１）を含むものである。金属Ｍを含む溶液としては、種々の工業廃液等を用いることができる。 In the method for producing a metal hydroxide according to the present embodiment, a solution containing a metal M and a solution or a suspension containing an alkaline agent (hereinafter, also referred to as "solution containing an alkaline agent") are continuously processed. It includes a step (1) of reacting a metal M with an alkaline agent to obtain a hydroxide of the metal M while supplying the metal M to a reaction vessel using the method. As the solution containing the metal M, various industrial waste liquids and the like can be used.
金属Ｍは、マグネシウム、アルミニウム、マンガン、亜鉛、鉄、カドミウム、コバルト、ニッケル、スズ、アンチモン、ビスマス、銅および銀からなる群から選ばれる少なくとも１種である。金属Ｍを含む溶液における金属Ｍの濃度としては、特に限定されず、例えば、０．０１～２０質量％であることが好ましく、０．１～１０質量％であることがより好ましい。金属Ｍを含む溶液における金属Ｍの濃度は、下記の実施例に記載の方法に準拠して求まるものである。 The metal M is at least one selected from the group consisting of magnesium, aluminum, manganese, zinc, iron, cadmium, cobalt, nickel, tin, antimony, bismuth, copper and silver. The concentration of the metal M in the solution containing the metal M is not particularly limited, and is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, for example. The concentration of the metal M in the solution containing the metal M can be obtained according to the method described in the following Examples.
アルカリ剤は、水酸化ナトリウム、水酸化カリウムおよび水酸化カルシウムからなる群から選ばれる少なくとも１種である。アルカリ剤を含む溶液等におけるアルカリ剤の濃度としては、特に限定されず、例えば、５～２０質量％であることが好ましく、１０～１５質量％であることがより好ましい。アルカリ剤として水酸化カルシウムを用いることで、金属Ｍがニッケルである場合、ニッケルの水酸化物を効果的に生成することができる。金属Ｍを含む溶液に対するアルカリ剤を含む溶液の質量割合としては、特に限定されず、例えば、１０～２００質量％であることが好ましく、１０～１００質量％であることがより好ましい。 The alkaline agent is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and calcium hydroxide. The concentration of the alkaline agent in the solution containing the alkaline agent is not particularly limited, and is preferably, for example, 5 to 20% by mass, more preferably 10 to 15% by mass. By using calcium hydroxide as an alkaline agent, when the metal M is nickel, a hydroxide of nickel can be effectively produced. The mass ratio of the solution containing the alkaline agent to the solution containing the metal M is not particularly limited, and is preferably, for example, 10 to 200% by mass, more preferably 10 to 100% by mass.
連続プロセス方式は、反応槽内に、金属Ｍを含む溶液を連続的に供給すると共に、アルカリ剤を含む溶液等を連続的または間欠的に供給し、金属Ｍの水酸化物を生成しつつ、金属Ｍの水酸化物を含む処理液を反応槽の外へ流出させる方式をいう。斯かる連続プロセス方式は、金属Ｍを含む溶液とアルカリ剤を含む溶液等との混合液を反応槽内に所定量で保持した状態で行われる。反応槽内に保持される混合液の量としては、特に限定されず、例えば、１０～５０００Ｌであることが好ましく、１０～２０００Ｌであることがより好ましい。 In the continuous process method, a solution containing a metal M is continuously supplied into the reaction vessel, and a solution containing an alkaline agent or the like is continuously or intermittently supplied to generate a hydroxide of the metal M. A method of allowing a treatment solution containing a hydroxide of metal M to flow out of the reaction vessel. Such a continuous process method is carried out in a state where a mixed solution of a solution containing a metal M and a solution containing an alkaline agent is held in a reaction vessel in a predetermined amount. The amount of the mixed solution held in the reaction vessel is not particularly limited, and is preferably 10 to 5000 L, more preferably 10 to 2000 L, for example.
連続プロセス方式における滞留時間（反応槽内の滞留時間）は、１～３０時間であり、２～３０時間であることが好ましい。滞留時間は、反応槽へ単位時間当たりに供給する金属Ｍを含む溶液の供給量（供給速度）と反応槽へ単位時間当たりに供給するアルカリ剤を含む溶液等の供給量（供給速度）との合計供給量で、反応槽内に保持される混合液の液量を除することで求まる。例えば、反応槽内に保持する混合液の液量が２Ｌであり、金属Ｍを含む溶液の供給速度とアルカリ剤を含む溶液等の供給速度との合計が０．２Ｌ／ｈである場合、滞留時間は１０時間となる。斯かる滞留時間は、金属Ｍを含む溶液の供給速度とアルカリ剤を含む溶液等の供給速度とを調整することで、設定することができる。 The residence time (residence time in the reaction vessel) in the continuous process method is 1 to 30 hours, preferably 2 to 30 hours. The residence time is the supply amount (supply rate) of the solution containing the metal M supplied to the reaction vessel per unit time and the supply amount (supply rate) of the solution containing the alkaline agent supplied to the reaction vessel per unit time. It is obtained by dividing the amount of the mixed solution held in the reaction vessel by the total supply amount. For example, when the amount of the mixed solution held in the reaction vessel is 2 L and the total of the supply rate of the solution containing the metal M and the supply rate of the solution containing the alkaline agent is 0.2 L / h, the retention is achieved. The time will be 10 hours. The residence time can be set by adjusting the supply rate of the solution containing the metal M and the supply rate of the solution containing the alkaline agent.
前記工程（１）を行う際のｐＨ（反応槽内の混合液のｐＨ）としては、特に限定されず、例えば、９～１３であることが好ましい。斯かるｐＨは、アルカリ剤を含む溶液等の反応槽への供給量を調節することで調整することができる。具体的には、反応槽内の混合液のｐＨを測定し、該測定結果に基づいて、アルカリ剤を含む溶液等の反応槽への供給量を調節することで上記のｐＨに調整することができる。 The pH (pH of the mixed solution in the reaction vessel) when performing the step (1) is not particularly limited, and is preferably 9 to 13, for example. Such pH can be adjusted by adjusting the supply amount of the solution containing the alkaline agent or the like to the reaction vessel. Specifically, the pH of the mixed solution in the reaction vessel can be measured, and the pH can be adjusted to the above pH by adjusting the supply amount of the solution containing the alkaline agent or the like to the reaction vessel based on the measurement result. can.
前記工程（１）は、硫酸、塩化ナトリウム、および、アンモニアからなる群から選ばれる少なくとも１種の添加剤の存在下で行うことができる。添加剤を含む溶液は、金属Ｍを含む溶液に添加して使用してもよく、反応槽内に添加して使用してもよい。添加剤の添加量としては、特に限定されず、例えば、単位時間当たりに反応槽へ供給されるアルカリ剤の供給量に対して０．５～３０質量％であることが好ましく、１～２０質量％であることがより好ましい。添加剤を用いることで、添加剤とアルカリ剤との反応によって、金属Ｍの水酸化物の粒子の核となる物質が反応槽内で形成される。具体的には、添加剤として硫酸を用い、アルカリ剤として水酸化カルシウムを用いた場合、核として硫酸カルシウムが生成する。そして、生成した核に金属Ｍの水酸化物が付着して成長することで金属Ｍの水酸化物の粒子を効率的に形成することができる。また、添加剤を用いることで、液状化し難い（ペースト状になり難い）金属Ｍの水酸化物を得ることができる。 The step (1) can be performed in the presence of at least one additive selected from the group consisting of sulfuric acid, sodium chloride, and ammonia. The solution containing the additive may be added to the solution containing the metal M and used, or may be added to the reaction vessel and used. The amount of the additive added is not particularly limited, and is preferably 0.5 to 30% by mass, preferably 1 to 20% by mass, based on the amount of the alkaline agent supplied to the reaction vessel per unit time. % Is more preferable. By using the additive, the substance that becomes the core of the hydroxide particles of the metal M is formed in the reaction vessel by the reaction between the additive and the alkaline agent. Specifically, when sulfuric acid is used as an additive and calcium hydroxide is used as an alkaline agent, calcium sulfate is produced as a nucleus. Then, the hydroxide particles of the metal M adhere to the generated nuclei and grow, so that the hydroxide particles of the metal M can be efficiently formed. Further, by using an additive, a hydroxide of metal M which is difficult to liquefy (difficult to form a paste) can be obtained.
上記のように構成される工程（１）を行うことで、金属Ｍの水酸化物の粒子が形成される。斯かる粒子の粒子径の標準偏差としては、特に限定されず、例えば、１０～８０であることが好ましく、１０～２０であることがより好ましい。標準偏差が上記の範囲であることで、粒子径の均一性に優れた粒子となる。このため、例えば、金属Ｍの水酸化物を原料として電極を形成すれば、平坦であり、短絡し難い電極等を得ることができる。具体的には、金属Ｍがニッケルである場合、工程（１）によって得られるニッケルの水酸化物は、リチウムイオン電池の正極の原料として利用できる。 By performing the step (1) configured as described above, the hydroxide particles of the metal M are formed. The standard deviation of the particle size of such particles is not particularly limited, and is preferably, for example, 10 to 80, more preferably 10 to 20. When the standard deviation is within the above range, the particles have excellent particle size uniformity. Therefore, for example, if an electrode is formed using a hydroxide of metal M as a raw material, an electrode that is flat and difficult to short-circuit can be obtained. Specifically, when the metal M is nickel, the hydroxide of nickel obtained in the step (1) can be used as a raw material for the positive electrode of the lithium ion battery.
また、斯かる粒子の平均粒子径としては、特に限定されず、例えば、４０～８０μｍであることが好ましく、６０～８０μｍであることがより好ましい。また、斯かる粒子の最大粒子径としては、特に限定されず、例えば、９０～３００μｍであることが好ましく、９０～１２０μｍであることがより好ましい。なお、平均粒子径および最大粒子径は、ＪＩＳ Ｚ ８８２７に規定する静的画像解析法に基づいて測定されるものである。 The average particle size of such particles is not particularly limited, and is preferably, for example, 40 to 80 μm, and more preferably 60 to 80 μm. The maximum particle size of such particles is not particularly limited, and is preferably 90 to 300 μm, more preferably 90 to 120 μm, for example. The average particle diameter and the maximum particle diameter are measured based on the static image analysis method specified in JIS Z 8827.
反応槽から流出する処理液は、ＪＩＳ Ｂ ８５３０（公害防止用語）の「２．（３）」に規定するＳＶ３０が３０～５０％であることが好ましく、３５～４５％であることがより好ましい。ＳＶ３０が上記の範囲であることで、金属Ｍの水酸化物の粒子の沈降性が比較的優れたものとなり、金属Ｍの水酸化物の生産性を向上させることができる。また、反応槽から流出する処理液は、ＪＩＳ Ｋ ０１０２（工場排水試験方法）の「１４．１ 懸濁物質」に規定する測定値を、金属Ｍの水酸化物を含むスラッジという性質上、便宜的にＳＳ（Ｓｕｓｐｅｎｄｉｄ Ｓｏｌｉｄｓ）と表現した場合、該ＳＳが３３０００～５３０００ｍｇ／Ｌであることが好ましく、３３０００～３７０００ｍｇ／Ｌであることがより好ましい。ＳＳが上記の範囲であることで、金属Ｍの水酸化物を含むスラッジの含水率が比較的少ないものとなり、スラッジを埋め立て処分等する際の処分量を低減するこができる。 The treatment liquid flowing out of the reaction vessel preferably has an SV30 of 30 to 50%, more preferably 35 to 45%, as defined in "2. (3)" of JIS B 8530 (pollution control term). .. When the SV30 is in the above range, the sedimentation property of the hydroxide particles of the metal M becomes relatively excellent, and the productivity of the hydroxide of the metal M can be improved. In addition, the treatment liquid flowing out of the reaction tank has the measured value specified in "14.1 Suspended solids" of JIS K 0102 (factory wastewater test method) for convenience due to the nature of sludge containing the hydroxide of metal M. When expressed as SS (Suspended Solids), the SS is preferably 33000 to 53000 mg / L, and more preferably 33000 to 37000 mg / L. When the SS is in the above range, the water content of the sludge containing the hydroxide of the metal M becomes relatively small, and the amount of sludge to be disposed of can be reduced when the sludge is landfilled.
反応槽から流出した処理液を固液分離することで、金属Ｍの水酸化物を含むスラッジを回収することができる。固液分離する方法としては、特に限定されず、例えば、沈降分離法、凝集分離法、各種濾材を用いた濾過方法等を用いることができる。そして、スラッジを脱水することで金属Ｍの水酸化物を含む脱水ケーキを得ることができる。脱水方法としては、特に限定されず、例えば、フィルタープレス、ベルトプレス、遠心分離機、デカンター等の公知の装置を用いることができる。 By solid-liquid separation of the treatment liquid flowing out of the reaction vessel, sludge containing the hydroxide of the metal M can be recovered. The method for solid-liquid separation is not particularly limited, and for example, a sedimentation separation method, a coagulation separation method, a filtration method using various filter media, or the like can be used. Then, by dehydrating the sludge, a dehydrated cake containing a hydroxide of metal M can be obtained. The dehydration method is not particularly limited, and for example, a known device such as a filter press, a belt press, a centrifuge, or a decanter can be used.
また、本実施形態に係る金属水酸化物の製造方法は、前記工程（１）に加えて、下記の工程（２）をさらに備えてもよい。
工程（２）：
前記工程（１）で得られた金属Ｍの水酸化物と、金属Ｍを含む溶液およびアルカリ剤（具体的には、水酸化カルシウム）を含む溶液または懸濁液から選択される少なくとも一方（具体的には、金属Ｍを含む溶液、または、アルカリ剤を含む溶液）と、を混合させて、金属Ｍの水酸化物を改質する工程
Further, the method for producing a metal hydroxide according to the present embodiment may further include the following step (2) in addition to the above step (1).
Step (2):
At least one selected from a solution or suspension containing the hydroxide of the metal M obtained in the step (1), the solution containing the metal M, and the alkaline agent (specifically, calcium hydroxide) (specifically). Specifically, a step of modifying a hydroxide of metal M by mixing it with a solution containing metal M or a solution containing an alkaline agent).
次に、上記のような金属水酸化物の製造方法を実施するための金属水酸化物の製造装置について、図面を参照しつつ説明する。なお、以下の図面において同一または相当する部分には同一の参照符号を付しその説明は繰り返さない。 Next, an apparatus for producing a metal hydroxide for carrying out the method for producing a metal hydroxide as described above will be described with reference to the drawings. In the following drawings, the same or corresponding parts are designated by the same reference numerals, and the description thereof will not be repeated.
本実施形態に係る金属水酸化物の製造装置１は、図１に示すように、金属Ｍを含む溶液を貯蔵する容器Ａと、アルカリ剤を含む溶液等を貯蔵する容器Ｂと、容器Ａから金属Ｍを含む溶液が供給され、容器Ｂからアルカリ剤を含む溶液等が供給され、金属Ｍとアルカリ剤とを反応させて金属Ｍの水酸化物を生成する反応槽Ｃと、反応槽Ｃから金属Ｍの水酸化物を含む処理液が供給される処理液槽Ｄとを備える。反応槽Ｃは、金属Ｍを含む溶液と、アルカリ剤を含む溶液等とを撹拌混合する撹拌翼Ｃ１を備える。 As shown in FIG. 1, the metal hydroxide producing apparatus 1 according to the present embodiment is composed of a container A for storing a solution containing a metal M, a container B for storing a solution containing an alkaline agent, and a container A. A solution containing the metal M is supplied, a solution containing an alkaline agent or the like is supplied from the container B, and the reaction tank C and the reaction tank C react the metal M with the alkaline agent to generate a hydroxide of the metal M. A treatment liquid tank D to which a treatment liquid containing a hydroxide of the metal M is supplied is provided. The reaction vessel C includes a stirring blade C1 that stirs and mixes a solution containing a metal M and a solution containing an alkaline agent or the like.
また、金属水酸化物の製造装置１は、容器Ａから反応槽Ｃへ金属Ｍを含む溶液を供給する供給管ＡＣと、容器Ｂから反応槽Ｃへアルカリ剤を含む溶液等を供給する供給管ＢＣと、反応槽Ｃから処理液層Ｄへ処理液を供給する供給管ＣＤとを備える。また、金属水酸化物の製造装置１は、供給管ＡＣにおける金属Ｍを含む溶液の流量を調節するポンプＰ１と、供給管ＢＣにおけるアルカリ剤を含む溶液等の流量を調節するポンプＰ２とを備える。また、金属水酸化物の製造装置１は、容器Ａ，Ｂから容器Ｃへ供給される液体の流量を計測する流量計Ｈを備える。 Further, the metal hydroxide manufacturing apparatus 1 includes a supply pipe AC for supplying a solution containing a metal M from the container A to the reaction tank C, and a supply pipe for supplying a solution containing an alkaline agent from the container B to the reaction tank C. A BC and a supply pipe CD for supplying the treatment liquid from the reaction tank C to the treatment liquid layer D are provided. Further, the metal hydroxide manufacturing apparatus 1 includes a pump P1 for adjusting the flow rate of the solution containing the metal M in the supply pipe AC and a pump P2 for adjusting the flow rate of the solution containing the alkaline agent in the supply pipe BC. .. Further, the metal hydroxide manufacturing apparatus 1 includes a flow meter H that measures the flow rate of the liquid supplied from the containers A and B to the container C.
また、本実施形態に係る金属水酸化物の製造装置１は、反応槽Ｃ内の混合液のｐＨを制御するｐＨコントローラーＦを備える。該ｐＨコントローラーＦは、混合液のｐＨを測定し、ｐＨが所定値となるように、容器Ｂから反応槽Ｃへのアルカリ剤を含む溶液等の供給量を調節する（具体的には、ポンプＰ２の流量を調節する）。 Further, the metal hydroxide producing apparatus 1 according to the present embodiment includes a pH controller F that controls the pH of the mixed solution in the reaction vessel C. The pH controller F measures the pH of the mixed solution and adjusts the supply amount of the solution containing the alkaline agent or the like from the container B to the reaction tank C so that the pH becomes a predetermined value (specifically, a pump). Adjust the flow rate of P2).
そして、金属水酸化物の製造装置１では、容器Ａから反応槽Ｃへの金属Ｍを含む溶液の供給、容器Ｂから反応槽Ｃへのアルカリ剤を含む溶液等の供給、反応槽Ｃから処理液槽Ｄへの処理液の供給は、連続プロセス方式にて実施される。これにより、連続プロセス方式によって、反応槽Ｃで、金属Ｍとアルカリ剤とを反応させて金属Ｍの水酸化物を生成しつつ、金属Ｍの水酸化物を含む処理液を反応槽Ｃから流出させて処理液槽Ｄに供給する。具体的には、容器Ａから反応槽Ｃへの溶液の供給を供給管ＡＣを介して連続的に行うと共に、容器Ｂから反応槽Ｃへの溶液等の供給を供給管ＢＣを介して連続的または断続的に行って、金属Ｍの水酸化物を生成しつつ、金属Ｍの水酸化物を含む処理液を反応槽Ｃから流出させて供給管ＣＤを介して処理液槽Ｄに供給する。この際、反応槽Ｃ内には、金属Ａを含む溶液とアルカリ剤を含む溶液との混合液を所定量で保持する。 Then, in the metal hydroxide manufacturing apparatus 1, the container A supplies the solution containing the metal M to the reaction vessel C, the container B supplies the solution containing the alkaline agent to the reaction vessel C, and the reaction vessel C processes. The treatment liquid is supplied to the liquid tank D by a continuous process method. As a result, the treatment liquid containing the hydroxide of the metal M flows out from the reaction tank C while reacting the metal M with the alkaline agent to form the hydroxide of the metal M in the reaction tank C by the continuous process method. And supply it to the processing liquid tank D. Specifically, the solution from the container A to the reaction tank C is continuously supplied via the supply pipe AC, and the solution or the like is continuously supplied from the container B to the reaction tank C via the supply pipe BC. Alternatively, the treatment liquid containing the metal M hydroxide is discharged from the reaction tank C and supplied to the treatment liquid tank D via the supply pipe CD while intermittently producing the metal M hydroxide. At this time, a predetermined amount of a mixed solution of the solution containing the metal A and the solution containing the alkaline agent is held in the reaction vessel C.
また、本実施形態に係る金属水酸化物の製造装置１は、容器Ａから反応槽Ｃへの金属Ｍを含む溶液の単位時間当たりの供給量（供給速度）と容器Ｂから反応槽Ｃへのアルカリ剤を含む溶液等の単位時間当たりの供給量（供給速度）とが、反応槽Ｃにおける滞留時間が１～３０時間（好ましくは、２～３０時間）となるように設定される。具体的には、金属水酸化物の製造装置１は、容器Ａから反応槽Ｃへの金属Ｍを含む溶液の供給速度と容器Ｂから反応槽Ｃへのアルカリ剤を含む溶液等の供給速度とを設定する供給速度設定部Ｇを備え、該供給速度設定部Ｇによって、反応槽Ｃ内に保持する混合液の液量に基づき、上記各供給速度（流量計Ｈで得られる流量）を設定することで、反応槽Ｃにおける滞留時間が１～３０時間（好ましくは、２～３０時間）となるように設定される。 Further, in the metal hydroxide manufacturing apparatus 1 according to the present embodiment, the supply amount (supply rate) of the solution containing the metal M from the container A to the reaction tank C per unit time and the supply amount (supply rate) from the container B to the reaction tank C. The supply amount (supply rate) per unit time of the solution containing the alkaline agent is set so that the residence time in the reaction tank C is 1 to 30 hours (preferably 2 to 30 hours). Specifically, the metal hydroxide producing apparatus 1 has a supply rate of a solution containing a metal M from a container A to a reaction tank C and a supply rate of a solution or the like containing an alkaline agent from the container B to the reaction tank C. The supply speed setting unit G is provided, and the supply speed setting unit G sets each of the above supply speeds (flow rate obtained by the flow meter H) based on the amount of the mixed solution held in the reaction tank C. Therefore, the residence time in the reaction vessel C is set to be 1 to 30 hours (preferably 2 to 30 hours).
また、本実施形態に係る金属水酸化物の製造装置１は、添加剤を含む溶液を貯蔵する容器Ｅを備え、該容器Ｅから反応槽Ｃまたは供給管ＢＣへ添加剤を含む溶液を供給可能に構成される。また、金属水酸化物の製造装置１は、容器Ｅから反応槽Ｃまたは供給管ＢＣへ添加剤を含む溶液を供給する供給管ＥＣまたは供給管ＥＢＣをさらに備えてもよい。 Further, the metal hydroxide manufacturing apparatus 1 according to the present embodiment includes a container E for storing a solution containing an additive, and the solution containing the additive can be supplied from the container E to the reaction tank C or the supply pipe BC. It is composed of. Further, the metal hydroxide producing apparatus 1 may further include a supply pipe EC or a supply pipe EBC that supplies a solution containing an additive from the container E to the reaction tank C or the supply pipe BC.
なお、本実施形態に係る金属水酸化物の製造方法、および、金属水酸化物の製造装置は、上記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の変更が可能である。また、上記以外の実施形態の構成や方法等を任意に採用して組み合わせてもよく、上記の１つの実施形態に係る構成や方法等を他の実施形態に係る構成や方法等に適用してもよい。 The method for producing a metal hydroxide and the apparatus for producing a metal hydroxide according to the present embodiment are not limited to the above-mentioned embodiment, and various changes can be made without departing from the gist of the present invention. It is possible. Further, the configurations and methods of embodiments other than the above may be arbitrarily adopted and combined, and the configurations and methods of one embodiment described above may be applied to the configurations and methods of other embodiments. May be good.
例えば、上記実施形態では、金属水酸化物の製造装置１は、供給管ＡＣ，ＢＣ，ＣＤを備えているが、これに限定されず、例えば、各供給管の少なくとも一つをＵ字溝等に代えた構成としてもよい。また、上記実施形態では、反応槽Ｃから流出する処理液は、供給管ＣＤを介して処理液槽Ｄに供給されるが、これに限定されず、例えば、図２に示すように、反応槽Ｃから直接、処理液槽Ｄへ供給されるように構成してもよい。 For example, in the above embodiment, the metal hydroxide manufacturing apparatus 1 includes supply pipes AC, BC, and CD, but the present invention is not limited to this, and for example, at least one of each supply pipe is provided with a U-shaped groove or the like. It may be configured instead of. Further, in the above embodiment, the treatment liquid flowing out of the reaction tank C is supplied to the treatment liquid tank D via the supply pipe CD, but the present invention is not limited to this, and for example, as shown in FIG. 2, the reaction tank is used. It may be configured to be supplied directly from C to the processing liquid tank D.
また、上記の金属水酸化物の製造方法において、工程（２）を行わないように構成してもよい。 Further, in the above-mentioned method for producing a metal hydroxide, the step (2) may not be performed.
以下、実施例及び比較例により、本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。
また、以下では、銅の濃度測定には、ＪＩＳ Ｋ ０１０２－５２．２（フレーム原子吸光法）を、ニッケルの濃度測定には、ＪＩＳ Ｋ ０１０２－５９．３（ＩＣＰ発光分光分析法）を、全クロムの濃度測定には、ＪＩＳ Ｋ ０１０２－６５．１．４（ＩＣＰ発光分光分析法）を用いた。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the following, JIS K 0102-52.2 (frame atomic absorption spectroscopy) will be used for copper concentration measurement, and JIS K 0102-59.3 (ICP emission spectroscopy) will be used for nickel concentration measurement. JIS K 0102-65.1.4 (ICP emission spectroscopy) was used to measure the concentration of total chromium.
［試験１］
＜実排液（金属Ｍを含む溶液）＞
下記２つの溶液を混合して、金属Ｍを含む溶液を作製した。該溶液中の銅（Ｃｕ）、全クロム（Ｔ－Ｃｒ）、ニッケル（Ｎｉ）の含有量は、下記表１に示す。
・溶液１：
ｐＨ＜１、Ｃｕ（４，５００ｍｇ／Ｌ）、Ｚｎ（２２０ｍｇ／Ｌ）、Ｎｉ（１，８００ｍｇ／Ｌ）、Ｆｅ（９，０００ｍｇ／Ｌ）、Ｍｎ（３４ｍｇ／Ｌ）、Ｔ－Ｃｒ（１，９００ｍｇ／Ｌ）、ＳＯ４
２－（３，５００ｍｇ／Ｌ）
・溶液２：
ｐＨ＜１、Ｆ（７，４００ｍｇ／Ｌ）、Ｂ（２，５００ｍｇ／Ｌ）、ＳＯ４
－（１４０ｍｇ／Ｌ）
[Test 1]
<Actual drainage (solution containing metal M)>
The following two solutions were mixed to prepare a solution containing metal M. The contents of copper (Cu), total chromium (T—Cr), and nickel (Ni) in the solution are shown in Table 1 below.
・ Solution 1:
pH <1, Cu (4,500 mg / L), Zn (220 mg / L), Ni (1,800 mg / L), Fe (9,000 mg / L), Mn (34 mg / L), T-Cr (1) , 900 mg / L), SO 4-2 ( 3,500 mg / L)
・ Solution 2:
pH <1, F (7,400 mg / L), B (2,500 mg / L), SO 4- ( 140 mg / L)
＜アルカリ剤を含む溶液＞
・アルカリ剤として水酸化カルシウムを用い、水酸化カルシウムの質量割合が１５質量％である水溶液（以下では、「１５ｗｔ％水酸化カルシウム液」とも記す）を作製した。
<Solution containing alkaline agent>
-Calcium hydroxide was used as an alkaline agent to prepare an aqueous solution having a mass ratio of calcium hydroxide of 15% by mass (hereinafter, also referred to as "15 wt% calcium hydroxide solution").
なお、以下の実施例及び比較例において、表中、「Ｃｕ」は、銅濃度を表し、「Ｎｉ」は、ニッケル濃度を表し、「Ｔ－Ｃｒ」は、全クロム濃度を表している。 In the following Examples and Comparative Examples, in the table, "Cu" represents the copper concentration, "Ni" represents the nickel concentration, and "T-Cr" represents the total chromium concentration.
［実施例１～４および比較例１］
上記実施形態の図１に示す装置１を用い、連続プロセス方式で、上記の実排液中の金属Ｍと１５％水酸化カルシウム液中の水酸化カルシウムとを反応させて金属Ｍを水酸化物として不溶化させると共に、その反応時間（滞留時間）を一定時間確保することで、不溶化した金属Ｍの水酸化物の粒子の改質を行った。
[Examples 1 to 4 and Comparative Example 1]
Using the apparatus 1 shown in FIG. 1 of the above embodiment, the metal M in the actual drainage liquid and the calcium hydroxide in the 15% calcium hydroxide liquid are reacted with each other by a continuous process method to hydroxide the metal M. The insolubilized metal M hydroxide particles were modified by insolubilizing them and ensuring the reaction time (residence time) for a certain period of time.
＜金属水酸化物の製造＞
具体的には、上記実施形態の図１に示す装置１を用い、反応槽Ｃ（樹脂製の容器であり、幾何容積３Ｌ、オーバーフローする容積（オーバーフローレベル）２Ｌ）中に、上記の実排液を仕込み、その上に１５ｗｔ％水酸化カルシウム液を添加してｐＨを１０．５に調整した。これにより、実排液と１５ｗｔ％水酸化カルシウム液との混合液（スラリー液）を形成し、該スラリー液で反応槽Ｃ内をオーバーフローレベルまで満たした。
<Manufacturing of metal hydroxides>
Specifically, using the apparatus 1 shown in FIG. 1 of the above embodiment, the above-mentioned actual drainage liquid is placed in the reaction tank C (a resin container having a geometric volume of 3 L and an overflow volume (overflow level) of 2 L). Was charged, and a 15 wt% calcium hydroxide solution was added thereto to adjust the pH to 10.5. As a result, a mixed liquid (slurry liquid) of the actual drainage liquid and the 15 wt% calcium hydroxide liquid was formed, and the inside of the reaction tank C was filled with the slurry liquid to the overflow level.
そして、スラリー液の攪拌を開始後、実排液の連続供給を開始すると共に、反応槽Ｃ内のｐＨが１０に維持されるよう、自動制御によって１５ｗｔ％水酸化カルシウム液を供給し、反応槽Ｃから処理液槽Ｄへスラリー液（処理液）をオーバーフローさせることで（換言すれば、連続プロセス方式で）、金属Ｍの水酸化物を製造した（金属Ｍの水酸化物を含むスラッジを得た）。自動制御は、反応槽Ｃ内に浸漬させたｐＨ電極の指示値から、ｐＨが９．５を下回った時に供給を開始し、ｐＨが１０．５を上回った時に供給を停止するという制御動作を、ｐＨコントローラーＦを用いて行った。反応時間（滞留時間）は、反応槽Ｃへの単位時間当たりの全供給量（即ち、実排液と１５ｗｔ％水酸化カルシウム液との単位時間当たりの合計供給量）が反応槽Ｃのオーバーフローする容積と同量となるまでの時間とした。例えば、実排液と１５ｗｔ％水酸化カルシウム液との合計供給量が１時間当たり２００ｍＬであり、オーバーフローレベルが２Ｌである場合の滞留時間は、１０時間となる。１５ｗｔ％水酸化カルシウム液の供給量は、あらかじめ実施した混合テストにおいて、実排液のｐＨが１０．５となる１５ｗｔ％水酸化カルシウム液の相当量を用いた。そして、実排液の供給開始後、滞留時間の３倍時間以上後の流出液（処理液）を採取し、１号ろ紙にて真空濾過した濾液を分析（金属濃度の測定）に供するサンプルとした。 Then, after starting the stirring of the slurry liquid, the continuous supply of the actual drainage liquid is started, and the 15 wt% calcium hydroxide liquid is supplied by automatic control so that the pH in the reaction tank C is maintained at 10, and the reaction tank is used. By overflowing the slurry liquid (treatment liquid) from C to the treatment liquid tank D (in other words, by a continuous process method), a hydroxide of metal M was produced (sludge containing the hydroxide of metal M was obtained). rice field). The automatic control is a control operation in which the supply is started when the pH falls below 9.5 and is stopped when the pH exceeds 10.5 from the indicated value of the pH electrode immersed in the reaction vessel C. , The pH controller F was used. As for the reaction time (residence time), the total supply amount per unit time to the reaction tank C (that is, the total supply amount of the actual drainage liquid and the 15 wt% calcium hydroxide solution per unit time) overflows in the reaction tank C. The time until the amount became the same as the volume was set. For example, when the total supply amount of the actual drainage solution and the 15 wt% calcium hydroxide solution is 200 mL per hour and the overflow level is 2 L, the residence time is 10 hours. As the supply amount of the 15 wt% calcium hydroxide solution, an equivalent amount of the 15 wt% calcium hydroxide solution having a pH of the actual drainage solution of 10.5 was used in the mixing test conducted in advance. Then, after the start of supply of the actual effluent, the effluent (treatment liquid) that is three times or more the residence time is collected, and the filtrate that has been evacuated with No. 1 filter paper is used for analysis (measurement of metal concentration). did.
＜ＳＶ３０、ＳＳ、ケーキ水分＞
下記表２に滞留時間と金属Ｍの水酸化物の粒子の改質結果を示す。
下記表２の「ＳＶ３０」は、処理液槽Ｄに供給された処理液（スラリー液）を３０分静置した後の沈殿物（スラッジ）の体積を表し、「ＳＳ」は、処理液槽Ｄに供給された処理液（スラリー液）中の浮遊物質量（即ち、金属水酸化物の懸濁液中に含まれるスラッジ発生量）を表し、「ケーキ水分」は、脱水処理後の固形物（スラッジ）中の水分量を表す。
なお、実施例及び比較例における上記測定項目は、上記の実施形態と同様に、ＪＩＳ Ｂ ８５３０（公害防止装置用語）及びＪＩＳ Ｋ ０１０２（工場排水試験方法）に準拠したものである。
<SV30, SS, cake moisture>
Table 2 below shows the residence time and the modification results of the hydroxide particles of metal M.
“SV30” in Table 2 below represents the volume of the precipitate (sludge) after the treatment liquid (slurry liquid) supplied to the treatment liquid tank D has been allowed to stand for 30 minutes, and “SS” represents the treatment liquid tank D. Represents the amount of suspended substances in the treatment liquid (slurry liquid) supplied to (that is, the amount of sludge generated in the suspension of metal hydroxide), and "cake moisture" is the solid matter after dehydration treatment (that is, the amount of sludge generated in the suspension of metal hydroxide). Represents the amount of water in the sludge).
The measurement items in the examples and comparative examples are based on JIS B 8530 (pollution control device term) and JIS K 0102 (factory wastewater test method) as in the above embodiment.
ＳＶ３０は、滞留時間０．１７時間で７４％、滞留時間１．０時間では３０％となり、滞留時間１．０時間以上でより低い値を示し、滞留時間２．５時間及び１０時間では４５％、滞留時間２０時間では３５％となり、滞留時間が長くなる程、沈降性が改善され（即ち、スラッジの沈降速度が速くなり）、滞留時間１．０時間以上ではその効果が平衡となることが分かった。 SV30 was 74% at a residence time of 0.17 hours and 30% at a residence time of 1.0 hour, showing lower values at a residence time of 1.0 hour or more, and 45% at a residence time of 2.5 hours and 10 hours. When the residence time is 20 hours, it becomes 35%, and as the residence time becomes longer, the settling property is improved (that is, the sedimentation rate of sludge becomes faster), and when the residence time is 1.0 hour or more, the effect becomes equilibrium. Do you get it.
ＳＳは、滞留時間０．１７時間で７４，８００ｍｇ／Ｌ、滞留時間１．０時間では５２，０００ｍｇ／Ｌとなり、滞留時間１．０時間以上でより低い値を示し、滞留時間２．５時間では３６，４００ｍｇ／Ｌとなり、さらに低い値を示し、滞留時間１０時間では３３，９００ｍｇ／Ｌ、滞留時間２０時間では３５，３００ｍｇ／Ｌとなり、ほぼ平衡に達した。滞留時間が長くなる程、ＳＳの低下（即ち、スラッジ発生量の削減）の効果が見られ、滞留時間２．５時間以上ではその効果が平衡となることが分かった。 SS was 74,800 mg / L with a residence time of 0.17 hours and 52,000 mg / L with a residence time of 1.0 hour, showing a lower value when the residence time was 1.0 hour or more, and the residence time was 2.5 hours. The value was 36,400 mg / L, which was even lower, 33,900 mg / L at a residence time of 10 hours, and 35,300 mg / L at a residence time of 20 hours, almost reaching equilibrium. It was found that the longer the residence time, the more the effect of lowering SS (that is, the reduction of the amount of sludge generated) was observed, and the effect became equilibrium when the residence time was 2.5 hours or more.
ケーキ水分は、滞留時間０．１７時間で７７．３％、滞留時間１．０時間では６９．７％、滞留時間２．５時間では６５．３％となり、滞留時間１．０時間以上でより低い値を示し、滞留時間１０時間では６５．５％、滞留時間２０時間では６３．８％となり、ほぼ平衡に達した。滞留時間が長くなる程、脱水ケーキ水分の低下（即ち、含有水分由来の重量におけるスラッジ発生量の削減）の効果が見られ、滞留時間２．５時間以上ではその効果が平衡となることが分かった。
下記表２に示すスラッジ発生量とは、処理液槽Ｄに供給された処理液（スラリー液）１Ｌ当たりの脱水後の水分を含んだケーキ（即ち、実排液から金属Ｍを水酸化物として固定化して脱水し、埋め立て処分等へ供される廃棄物とし得るもの）の量を示す。スラッジ発生量は、下記（１）式から算出する。
スラッジ発生量（ＷＥＴベース）［ｇ／Ｌ］＝
ＳＳ［ｍｇ／Ｌ］×１００／（１００－ケーキ水分［％］）／１０００…（１）
The cake water content was 77.3% with a residence time of 0.17 hours, 69.7% with a residence time of 1.0 hour, and 65.3% with a residence time of 2.5 hours. It showed a low value, 65.5% at a residence time of 10 hours, and 63.8% at a residence time of 20 hours, almost reaching equilibrium. It was found that the longer the residence time, the more the effect of reducing the water content of the dehydrated cake (that is, the reduction of the amount of sludge generated in the weight derived from the water content) was observed, and the effect became equilibrium when the residence time was 2.5 hours or more. rice field.
The sludge generation amount shown in Table 2 below is a cake containing dehydrated water per 1 L of the treatment liquid (slurry liquid) supplied to the treatment liquid tank D (that is, metal M is used as a hydroxide from the actual drainage liquid). The amount of waste that can be immobilized, dehydrated, and used for landfill disposal, etc.) is shown. The amount of sludge generated is calculated from the following equation (1).
Sludge generation amount (WET base) [g / L] =
SS [mg / L] x 100 / (100-cake moisture [%]) / 1000 ... (1)
処理液槽Ｄに供給された処理液（スラリー液）中のＣｕの濃度は、滞留時間０．１７時間で２．３ｍｇ／Ｌ、滞留時間１．０時間で３．１ｍｇ／Ｌであった。滞留時間２．５時間、１０時間、２０時間で、各金属（Ｃｕ、Ｎｉ、Ｔ－Ｃｒ）の濃度は、１ｍｇ／Ｌ未満であり、好適に処理（不溶化）され、滞留時間が長い程、良好な処理効果が得られることが分かった。
The concentration of Cu in the treatment liquid (slurry liquid) supplied to the treatment liquid tank D was 2.3 mg / L with a residence time of 0.17 hours and 3.1 mg / L with a residence time of 1.0 hour. With a residence time of 2.5 hours, 10 hours, and 20 hours, the concentration of each metal (Cu, Ni, T—Cr) is less than 1 mg / L, and the treatment (insolubilization) is suitable, and the longer the residence time, the more. It was found that a good treatment effect was obtained.
滞留時間毎の金属Ｍの水酸化物の粒子径は、下記表３に示す通り、滞留時間が短い程、最小粒子径が小さく最大粒子径が大きい（即ち、粒子径のバラツキ（標準偏差）が大きかった）。これとは逆に、滞留時間が長くなるに従い、粒子径のバラツキ（標準偏差）が小さくなり、概ね、滞留時間２．５時間以上からほぼ平衡に達した。
これについて、理論的には、粒子の沈降速度はストークスの式に従い、粒子径が大きくなるほど沈降速度が速くなる。
ストークスの式：Ｄｐ
２（ρｐ－ρｆ）ｇ／１８η
（ここで、Ｄｐ：粒子径、ρｐ：粒子密度、ρｆ：流体密度、ｇ：重力加速度、η：流体粘度）
ストークスの式から分かるように、沈降速度は、粒子径の２乗に比例する。即ち、粒子が大きくなるほど沈降性が速くなる。一方、本件実施例では、粒子が小さく粒揃いである方が沈降性が速くなった。これは、滞留時間の短い時に生じる結合水を多く含むゲル状のスラッジに比べ、滞留時間を長くすることで結合水が少ないスラッジが形成され（脱水縮合が促進され）、スラッジの粘性等が低下したことによって、沈降性が改善されたものと考えられる。
As shown in Table 3 below, the shorter the residence time, the smaller the minimum particle size and the larger the maximum particle size (that is, the variation (standard deviation) in the particle size) of the hydroxide particle size of the metal M for each residence time. It was big). On the contrary, as the residence time became longer, the variation (standard deviation) in the particle size became smaller, and the equilibrium was almost reached from the residence time of 2.5 hours or more.
In this regard, theoretically, the settling velocity of particles follows Stokes' equation, and the larger the particle size, the faster the settling velocity.
Stokes' equation: D p 2 (ρ p −ρ f ) g / 18η
(Here, D p : particle diameter, ρ p : particle density, ρ f : fluid density, g: gravitational acceleration, η: fluid viscosity)
As can be seen from Stokes' equation, the sedimentation velocity is proportional to the square of the particle size. That is, the larger the particles, the faster the sedimentation property. On the other hand, in the present embodiment, the smaller the particles and the more uniform the particles, the faster the sedimentation property. Compared to gel-like sludge containing a large amount of bound water that occurs when the residence time is short, sludge with less bound water is formed by lengthening the residence time (dehydration condensation is promoted), and the viscosity of the sludge is reduced. It is considered that the sedimentation property was improved by the above.
［試験２］
＜実施例５＞連続プロセス方式（硫酸あり）
硫酸を添加した下記モデル排液Ａを用い、実施例１と同様に、連続プロセス方式での反応を行った。
［モデル排液Ａ］
（１）蒸留水約３Ｌ中に塩化ニッケル（ＩＩ）６水和物２０８．７ｇを加え、よく攪拌して溶解させた。
（２）前記（１）で得られた溶液に、７０質量％硫酸を４４．２ｍＬ加え、よく攪拌して溶解させた。
（３）前記（２）で得られた溶液に、蒸留水を加えて全容量を５Ｌにした。
[Test 2]
<Example 5> Continuous process method (with sulfuric acid)
Using the following model effluent A to which sulfuric acid was added, the reaction was carried out by a continuous process method in the same manner as in Example 1.
[Model drainage A]
(1) 208.7 g of nickel (II) chloride hexahydrate was added to about 3 L of distilled water, and the mixture was well stirred and dissolved.
(2) To the solution obtained in (1) above, 44.2 mL of 70% by mass sulfuric acid was added, and the mixture was well stirred and dissolved.
(3) Distilled water was added to the solution obtained in (2) above to bring the total volume to 5 L.
モデル排液Ａについて、実施例１と同様に、モデル排液Ａを反応槽Ｃへ連続供給し、設定ｐＨの１０．５となるように１５ｗｔ％水酸化カルシウム液を添加し、その滞留時間を９時間として、連続プロセス方式で、金属水酸化物（水酸化ニッケル）の製造を行い、ＳＶ３０、ＳＳ、ケーキ水分、および、スラッジ発生量を求めた。その結果、ＳＶ３０が１３％、ＳＳが２８，７００ｍｇ／Ｌ、ケーキ水分が７３．８％となった。また、スラッジ発生量は、上記の（１）式で求めた結果、１１０ｇ／Ｌとなった。また、脱水ケーキの液状化の有無について、脱水ケーキを手で強く揉むことで液状化するか評価した結果、液状化しなかった。なお、「液状化した」とは、脱水ケーキがペースト状になることをいい、「液状化しない」とは、脱水ケーキがペースト状にならず粒状を維持することをいう。 Regarding the model drainage A, the model drainage A is continuously supplied to the reaction tank C in the same manner as in Example 1, a 15 wt% calcium hydroxide solution is added so as to have a set pH of 10.5, and the residence time thereof is adjusted. Metal hydroxide (nickel hydroxide) was produced by a continuous process method for 9 hours, and SV30, SS, cake water content, and sludge generation amount were determined. As a result, SV30 was 13%, SS was 28,700 mg / L, and cake water content was 73.8%. The amount of sludge generated was 110 g / L as a result of the above equation (1). Further, as a result of evaluating whether or not the dehydrated cake was liquefied by strongly rubbing the dehydrated cake by hand, it was not liquefied. In addition, "liquefied" means that the dehydrated cake becomes a paste, and "not liquefied" means that the dehydrated cake does not become a paste and remains granular.
＜実施例６＞連続プロセス方式（硫酸なし）
硫酸を添加しない下記モデル排液Ｂを用い、実施例１と同様に、連続プロセス方式での反応を行った。
［モデル排液Ｂ］
（１）蒸留水約３Ｌ中に塩化ニッケル（ＩＩ）６水和物２０８．７ｇを加え、よく攪拌して溶解させた。
（２）前記（１）で得られた溶液に、蒸留水を加えて全容量を５Ｌにした。
<Example 6> Continuous process method (without sulfuric acid)
Using the following model effluent B to which sulfuric acid was not added, the reaction was carried out by a continuous process method in the same manner as in Example 1.
[Model drainage B]
(1) 208.7 g of nickel (II) chloride hexahydrate was added to about 3 L of distilled water, and the mixture was well stirred and dissolved.
(2) Distilled water was added to the solution obtained in (1) above to bring the total volume to 5 L.
モデル排液Ｂについて、実施例２と同様に、モデル排液Ｂを反応槽Ｃへ連続供給し、設定ｐＨの１０．５となるように１５ｗｔ％水酸化カルシウム液を添加し、その滞留時間を９時間として、連続プロセス方式で、金属水酸化物（水酸化ニッケル）の製造を行い、ＳＶ３０、ＳＳ、ケーキ水分、および、スラッジ発生量を求めた。その結果、ＳＶ３０が９％、ＳＳが１９，９５０ｍｇ／Ｌ、ケーキ水分が８２．９％となった。また、スラッジ発生量は、上記の（１）式で求めた結果、１１７ｇ／Ｌとなった。また、液状化の有無について、実施例５と同様に評価した結果、液状化が起こった。 Regarding the model drainage B, as in Example 2, the model drainage B is continuously supplied to the reaction vessel C, a 15 wt% calcium hydroxide solution is added so as to have a set pH of 10.5, and the residence time thereof is adjusted. Metal hydroxide (nickel hydroxide) was produced by a continuous process method for 9 hours, and SV30, SS, cake water content, and sludge generation amount were determined. As a result, SV30 was 9%, SS was 19,950 mg / L, and cake water content was 82.9%. Further, the sludge generation amount was 117 g / L as a result of obtaining by the above formula (1). Further, as a result of evaluating the presence or absence of liquefaction in the same manner as in Example 5, liquefaction occurred.
下記表４および５に、上記の実施例５、実施例６の試験結果を示す。
各モデル排液を連続供給し、連続プロセス方式を用いることで、沈降性が良く、ケーキ水分とスラッジ発生量が小さいことが認められた。滞留時間毎の金属Ｍの水酸化物（水酸化ニッケル）の粒子径は、粒子径のバラツキ（標準偏差）が小さいことが認められた。さらに、硫酸を添加することで液状化しない強固な水酸化ニッケルケーキを得ることができた。
Tables 4 and 5 below show the test results of Examples 5 and 6 above.
It was confirmed that the sedimentation property was good and the amount of cake water and sludge generated was small by continuously supplying each model drainage and using the continuous process method. It was found that the particle size of the hydroxide (nickel hydroxide) of the metal M for each residence time had a small variation (standard deviation) in the particle size. Furthermore, by adding sulfuric acid, a strong nickel hydroxide cake that did not liquefy could be obtained.
Claims (13)
工程（１）：
マグネシウム、アルミニウム、マンガン、亜鉛、鉄、カドミウム、コバルト、ニッケル、スズ、アンチモン、ビスマス、銅および銀からなる群から選ばれる少なくとも１種の金属Ｍを含む溶液と、水酸化ナトリウム、水酸化カリウムおよび水酸化カルシウムからなる群から選ばれる少なくとも１種のアルカリ剤を含む溶液または懸濁液とを、連続プロセス方式を用いて、反応槽に供給しつつ、滞留時間が１～３０時間の条件で、金属Ｍとアルカリ剤とを反応させて、金属Ｍの水酸化物を得る工程
A method for producing a metal hydroxide, which comprises the following step (1).
Step (1):
A solution containing at least one metal M selected from the group consisting of magnesium, aluminum, manganese, zinc, iron, cadmium, cobalt, nickel, tin, antimony, bismuth, copper and silver, and sodium hydroxide, potassium hydroxide and A solution or suspension containing at least one alkaline agent selected from the group consisting of calcium hydroxide is supplied to the reaction vessel by a continuous process method, and the residence time is 1 to 30 hours. Step of reacting metal M with an alkaline agent to obtain hydroxide of metal M
工程（２）：
前記工程（１）で得られた金属Ｍの水酸化物と、前記金属Ｍを含む溶液および前記アルカリ剤を含む溶液または懸濁液から選択される少なくとも一方と、を混合させて、金属Ｍの水酸化物を改質する工程
The method for producing a metal hydroxide according to any one of claims 1 to 9, further comprising the following step (2).
Step (2):
The hydroxide of the metal M obtained in the step (1) is mixed with at least one selected from the solution containing the metal M and the solution or suspension containing the alkaline agent to obtain the metal M. Step to modify hydroxide
水酸化ナトリウム、水酸化カリウムおよび水酸化カルシウムからなる群から選ばれる少なくとも１種のアルカリ剤を含む溶液または懸濁液を貯蔵する容器Ｂと、
容器Ａから金属Ｍを含む溶液が供給され、容器Ｂからアルカリ剤を含む溶液または懸濁液が供給され、金属Ｍとアルカリ剤とを反応させて金属Ｍの水酸化物を生成する反応槽Ｃと、
反応槽Ｃから金属Ｍの水酸化物を含む処理液が供給される処理液槽Ｄと、
を備え、
容器Ａから反応槽Ｃへの溶液の供給、容器Ｂから反応槽Ｃへの溶液または懸濁液の供給、反応槽Ｃから処理液槽Ｄへの処理液の供給は、連続プロセス方式にて実施され、
容器Ａから反応槽Ｃへの溶液の単位時間当たりの供給量と容器Ｂから反応槽Ｃへの溶液または懸濁液の単位時間当たりの供給量とが、反応槽Ｃにおける滞留時間が１～３０時間となるように設定されている金属水酸化物の製造装置。 A container A for storing a solution containing at least one metal M selected from the group consisting of magnesium, aluminum, manganese, zinc, iron, cadmium, cobalt, nickel, tin, antimony, bismuth, copper and silver.
A container B for storing a solution or suspension containing at least one alkaline agent selected from the group consisting of sodium hydroxide, potassium hydroxide and calcium hydroxide.
A reaction tank C in which a solution containing a metal M is supplied from the container A, a solution or a suspension containing an alkaline agent is supplied from the container B, and the metal M and the alkaline agent are reacted to form a hydroxide of the metal M. When,
The treatment liquid tank D to which the treatment liquid containing the hydroxide of the metal M is supplied from the reaction tank C, and
Equipped with
The supply of the solution from the container A to the reaction tank C, the supply of the solution or suspension from the container B to the reaction tank C, and the supply of the treatment liquid from the reaction tank C to the treatment liquid tank D are carried out by a continuous process method. Being done
The supply amount of the solution from the container A to the reaction tank C per unit time and the supply amount of the solution or suspension from the container B to the reaction tank C per unit time are 1 to 30 in the reaction tank C. Metal hydroxide production equipment set to time.
硫酸または塩化ナトリウムを含む溶液を容器Ｅから反応槽Ｃへ供給する、
請求項１１または１２に記載の金属水酸化物の製造装置。 Further, a container E for storing a solution containing sulfuric acid or sodium chloride is provided.
Supplying a solution containing sulfuric acid or sodium chloride from vessel E to reaction vessel C,
The apparatus for producing a metal hydroxide according to claim 11 or 12.
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| JPH026340A (en) * | 1988-04-13 | 1990-01-10 | Kansai Shokubai Kagaku Kk | Production of nickel hydroxide |
| JPH04325414A (en) * | 1991-04-25 | 1992-11-13 | Sumitomo Chem Co Ltd | Production of zinc oxide-zinc hydroxide mixture |
| JPH1097856A (en) * | 1996-09-20 | 1998-04-14 | Tanaka Kagaku Kenkyusho:Kk | Nickel hydroxide for alkaline storage batteries and method for producing the same |
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| JP2018016531A (en) * | 2016-07-29 | 2018-02-01 | ユミコア | Highly efficient method for producing composite metal hydroxide particles |
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