JPH0120213B2

JPH0120213B2 -

Info

Publication number: JPH0120213B2
Application number: JP59062432A
Authority: JP
Inventors: Kazuhiro Uchino; Toshio Watanabe; Minoru Hoshino
Original assignee: Shingijutsu Kaihatsu Jigyodan; Kawasaki Steel Corp
Current assignee: JFE Steel Corp; Shingijutsu Kaihatsu Jigyodan
Priority date: 1984-03-30
Filing date: 1984-03-30
Publication date: 1989-04-14
Also published as: JPS60208429A

Description

【発明の詳細な説明】本発明は、金属イオンを抽出含有する有機溶媒
と弗化物系剥離液とを混合接触させて、金属弗化
物または金属錯体結晶を析出させ、かつ剥離後の
有機溶媒と剥離液とを分離する装置に関するもの
である。Detailed Description of the Invention The present invention involves mixing and contacting an organic solvent containing an extracted metal ion with a fluoride-based stripping solution to precipitate a metal fluoride or metal complex crystal, and then removing the organic solvent after stripping. The present invention relates to a device that separates the stripping liquid from the stripping liquid.

近年、高純度の金属や金属酸化物を得る方法と
して注目されている溶媒抽出法は、精製工程が簡
単でかつエネルギー消費も少ない方法として評価
されている。また、抽出の対象となる金属も
Mg、Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、
Cd、Nb、Zr、Ta、Mo、Ｗ、Inなど多くに及ん
でいる。 In recent years, solvent extraction has attracted attention as a method for obtaining high-purity metals and metal oxides, and has been praised as a method with a simple purification process and low energy consumption. Also, the metals that can be extracted are
Mg, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn,
These include Cd, Nb, Zr, Ta, Mo, W, In, and many others.

溶媒抽出法で従来問題であつたこれらの金属イ
オンの剥離（逆抽出）方法については、弗化物系
剥離液（HF、NH₄HF₂、NH₄Fの１種または２
種以上を含有する水溶液）を用いることで解決が
つき（特開昭57−42545、特開昭57−73138、特開
昭57−73141、特開昭57−85943号公報参照）、そ
れに用いる晶析装置も提案されている。特開昭58
−81402号公報に示されているものは逆円錐型の
晶析装置であつて、クリスタルオスロー型（分級
流動層型）を改良して結晶生成条件をより安定化
させたものであり、逆円錐型とすることにより製
品結晶の粒度がきわめて均一性にすぐれたものを
与える。 Regarding the stripping (reverse extraction) method of these metal ions, which has traditionally been a problem with solvent extraction methods, fluoride-based stripping solutions (HF, NH ₄ HF ₂ , NH ₄ F) or
The solution can be found by using an aqueous solution containing more than one species (see JP-A-57-42545, JP-A-57-73138, JP-A-57-73141, JP-A-57-85943), and the crystals used therein. Analyzers have also been proposed. Unexamined Japanese Patent Publication 1983
The device shown in Publication No. 81402 is an inverted cone type crystallizer, which is an improved version of the Crystal Oslo type (classified fluidized bed type) to make the crystal formation conditions more stable. By molding, the grain size of the product crystals becomes extremely uniform.

しかるに、上記晶析装置については、従来、実
験室規模の実施例しかなく、本発明者らにおい
て、第１図に示すような結晶生産能力45トン／月
の工業的規模の装置で実施したところ、実施例１
に示すような析出結晶の器壁への付着や装置下部
における堆積・固化あるいは結晶スラリーへの有
機溶媒の取り込みなど、装置の連続運転に支障を
来たすような現象が発生した。 However, the above-mentioned crystallization apparatus has so far only been implemented on a laboratory scale, and the present inventors have conducted experiments using an industrial scale apparatus with a crystal production capacity of 45 tons/month as shown in Figure 1. , Example 1
Phenomena that interfered with the continuous operation of the device occurred, such as adhesion of precipitated crystals to the vessel walls, deposition and solidification at the bottom of the device, and incorporation of organic solvent into the crystal slurry, as shown in (a).

本発明の目的は、かかる逆円錐型晶析装置の構
造に起因する欠点を解消し、従来装置の優れた分
級特性を生かしつつ連続運転を容易ならしめる金
属剥離用晶析装置を提供することにある。 An object of the present invention is to provide a crystallizer for metal stripping that eliminates the drawbacks caused by the structure of such an inverted conical crystallizer and facilitates continuous operation while taking advantage of the excellent classification characteristics of the conventional device. be.

本発明は、金属イオンを抽出含有する有機溶媒
と加温された弗化物系剥離液とを混合接触させて
金属イオンを弗化物または弗化物錯体として剥離
（逆抽出）させるための逆円錐形晶析装置におい
て、前記逆円錐形装置本体下部に設けられ、外部
の熱交換器と接続された冷却ゾーンと、この冷却
ゾーン中に設けられ、その最下部に剥離液に旋回
流を起させるため、ほぼ接線方向に配向された少
なくとも１個の吹き出しノズルを有する強制循環
ゾーンとを備えることを特徴とする金属剥離用晶
析装置を提供するものである。 The present invention is an inverted conical crystal for extracting metal ions and stripping (back-extracting) metal ions as fluorides or fluoride complexes by bringing them into mixed contact with an organic solvent containing a heated fluoride stripping solution. In the analysis apparatus, a cooling zone is provided at the bottom of the inverted cone-shaped apparatus body and connected to an external heat exchanger, and a cooling zone is provided in the cooling zone to cause a swirling flow in the stripping liquid at the lowest part of the cooling zone. a forced circulation zone having at least one blowing nozzle oriented substantially tangentially.

本発明の詳細を図面に基づき詳細に説明する
が、本発明はこれに限定されるものではない。第
１図が従来装置の一例を示すのに対し、第２図お
よび第３図は本発明の装置例を示す。 The details of the present invention will be explained in detail based on the drawings, but the present invention is not limited thereto. While FIG. 1 shows an example of a conventional device, FIGS. 2 and 3 show examples of the device of the present invention.

金属イオンを抽出含有する有機溶媒２は温度調
節器３を経て、NH₄HF₂等から成る弗化物系剥
離液４は加熱器５を経て、それぞれ混合槽６に導
入され、ここで撹拌装置７により混合されて有機
相２中の金属イオンは弗化物または弗化金属アン
モニウム塩として水相４中に剥離される。有機溶
媒および剥離液を温度調節するのは次の理由によ
る。 The organic solvent 2 containing extracted metal ions passes through a temperature controller 3, and the fluoride stripping solution 4 consisting of NH ₄ HF ₂ etc. passes through a heater 5 and is introduced into a mixing tank 6, where a stirring device 7 The metal ions in the organic phase 2 are exfoliated into the aqueous phase 4 as fluoride or metal ammonium fluoride salt. The reason for controlling the temperature of the organic solvent and stripping solution is as follows.

金属イオンの剥離により比重の増大した水相４
は、下降管８中を有機溶媒を分離し、かつ溶解度
の比較的小さい弗化物または弗化金属アンモニウ
ム塩の結晶を析出しつつ下降する。本発明におい
ては、下降管８の下端は従来の第１図に示すよう
に本体１の下端付近まで延長せず、後述する冷却
ゾーン１０の上限にあたる冷却剥離液排出口１１
の位置より上部にあつて、下降する剥離液および
結晶に附随する有機溶媒の分離をよくするように
配慮されている。 Aqueous phase 4 with increased specific gravity due to detachment of metal ions
descends in the downcomer pipe 8 while separating the organic solvent and precipitating crystals of fluoride or metal ammonium fluoride salt having relatively low solubility. In the present invention, the lower end of the downcomer pipe 8 does not extend to the vicinity of the lower end of the main body 1 as shown in the conventional FIG.
It is located above the position of , and is designed to improve the separation of the descending stripping solution and the organic solvent accompanying the crystals.

有機溶媒は混合槽６から溢流して静置区域１２
に分離され、溢流せき１３を経て有機溶媒排出口
１４より排出される。下降管８を下降した剥離液
および結晶は冷却ゾーン１０に導かれる。冷却ゾ
ーン１０は冷却剥離液排出口１１および導入口１
５を通じてポンプ１６および熱交換器１７と接続
されており、混合槽６で加温状態にあつた剥離液
を冷却することにより結晶の成長が促進されると
ともに、一部結晶の分級も行われる。 The organic solvent overflows from the mixing tank 6 and enters the standing area 12.
The organic solvent is separated and discharged from an organic solvent outlet 14 via an overflow weir 13. The stripping liquid and crystals that have descended down the downcomer pipe 8 are guided to a cooling zone 10. The cooling zone 10 has a cooling stripping liquid outlet 11 and an inlet 1.
It is connected to a pump 16 and a heat exchanger 17 through a mixing tank 6, and by cooling the stripping liquid heated in a mixing tank 6, the growth of crystals is promoted, and some of the crystals are also classified.

さらに、冷却ゾーン１０の内部には強制循環ゾ
ーン１８が設けられている。強制循環ゾーンは循
環剥離液排出口１９、ポンプ２０、循環液吹き出
しノズル２１と接続されており、第３図の例に示
すような同一平面内に１か所以上（図面では２ケ
所）配置された吹き出しノズル２１からの流れに
より旋回流を起すことにより、結晶スラリーに流
動性を与えつつ剥離液の温度と濃度・組成を均一
に保ち、よつて結晶の器壁への付着や冷却ゾーン
１０の下部における堆積固化を防止することがで
きる。さて、剥離液４は下降管８を下降した後、
最終的には結晶分離ゾーン２２を上昇し、溢流せ
き２３を経て剥離液排出口２４より装置外に排出
される。また、結晶は結晶排出管２５からスラリ
ーとして適宜排出され、固液分離にかけられる。
なお、吹き出しノズル２１は旋回流を形成させる
ことができればよく、好ましくは接線方向に配向
され、１個以上あれば良い。 Furthermore, a forced circulation zone 18 is provided inside the cooling zone 10. The forced circulation zone is connected to the circulating stripping liquid outlet 19, the pump 20, and the circulating liquid blowing nozzle 21, and is arranged at one or more locations (two locations in the drawing) within the same plane as shown in the example of FIG. By generating a swirling flow with the flow from the blowing nozzle 21, the temperature, concentration, and composition of the stripping solution are kept uniform while giving fluidity to the crystal slurry, thereby preventing crystals from adhering to the vessel wall and cooling zone 10. It is possible to prevent accumulation and solidification in the lower part. Now, after the stripping liquid 4 descends through the downcomer pipe 8,
Finally, the liquid rises through the crystal separation zone 22, passes through the overflow weir 23, and is discharged from the stripping liquid outlet 24 to the outside of the apparatus. Further, the crystals are appropriately discharged as a slurry from the crystal discharge pipe 25 and subjected to solid-liquid separation.
Note that the blow-off nozzle 21 only needs to be able to form a swirling flow, preferably oriented in the tangential direction, and one or more blow-off nozzles 21 may be provided.

以上説明したように、従来装置で下降管の短い
型を採用し、新たに冷却ゾーン内に強制循環ゾー
ンを設けることにより、析出結晶の器壁への付着
や装置下部における堆積・固化を防止し、結晶ス
ラリーへの有機溶媒の取り込みを抑制することが
でき、装置の連続運転を容易に遂行することがで
きる。 As explained above, by adopting a short downcomer pipe in the conventional equipment and installing a new forced circulation zone within the cooling zone, it is possible to prevent precipitated crystals from adhering to the vessel wall and from accumulating and solidifying at the bottom of the equipment. , the incorporation of organic solvent into the crystal slurry can be suppressed, and continuous operation of the apparatus can be easily achieved.

以下に、本発明の実施例につき具体的に説明す
る。 Examples of the present invention will be specifically described below.

実施例１ 30V／Ｖ％D2EHPA（ジ―２―エチルヘキシル
燐酸）と70V／Ｖ％ｎ―パラフインから成る有機
溶媒でFe³⁺イオンを17.6ｇ/抽出含有するもの
（21℃）を、２m³／時の割合で、第１図に示す従
来装置の混合槽６に導入した。剥離液として
NH₄HF₂の125ｇ/溶液（46℃）を3.5m³／時の
割合で混合槽６に導入し、（NH₄）₃FeF₆結晶を析
出させた。この従来型装置では下半部全域にわた
つて結晶の器壁や下降管８への付着が見られ、ま
た装置下部においては結晶の堆積・固化を生じ、
運転開始後３日目にして運転続行が困難となつ
た。また下降管８の下端が装置底部にまで延びて
いるため、そこから有機溶媒の液滴が上昇し、そ
の一部は冷却剥離液排出口１１より吸引されて結
晶スラリーに取り込まれる結果となつた。分析の
結果、結晶のＰ含有率は２〜３％であつた。Example 1 An organic solvent consisting of 30V/V% D2EHPA (di-2-ethylhexyl phosphoric acid) and 70V/V% n-paraffin containing 17.6g/extracted Fe ³⁺ ions (at 21°C) was prepared at 2 m ³ / was introduced into the mixing tank 6 of the conventional apparatus shown in FIG. As a stripping liquid
125 g/solution (46° C.) of NH ₄ HF ₂ was introduced into the mixing tank 6 at a rate of 3.5 m ³ /hour to precipitate (NH ₄ ) ₃ FeF ₆ crystals. In this conventional device, crystals were observed to adhere to the vessel wall and downcomer pipe 8 throughout the lower half, and crystals were deposited and solidified in the lower part of the device.
On the third day after the start of operation, it became difficult to continue operation. In addition, since the lower end of the downcomer pipe 8 extended to the bottom of the apparatus, droplets of organic solvent rose from there, and some of them were sucked through the cooling stripper outlet 11 and incorporated into the crystal slurry. . As a result of analysis, the P content of the crystals was 2 to 3%.

実施例２実施例１と同じ組成の有機溶媒でFe³⁺イオン
を18.7ｇ/抽出含有するもの（23℃）を、２
m³／時の割合で、第２図に示す本発明の装置に導
入し、125ｇ/NH₄HF₂剥離液（45℃）を3.5
m³／時の割合で導入し、（NH₄）₃FeF₆結晶を析出
させた。この本発明の装置では、運転開始後24日
間経過しても結晶の器壁への付着や装置下部への
堆積・固化がほとんど見られなかつた。また下降
管８の下端が冷却ゾーン１０の上限よりも上にあ
るため、結晶スラリーへの有機溶媒の取り込みが
少なく、分析の結果、結晶のＰ含有率は0.31〜
0.60％であつた。Example 2 An organic solvent with the same composition as in Example 1 containing 18.7 g/extracted Fe ³⁺ ions (at 23°C) was
m ³ _/ h into the apparatus of the present invention _shown in FIG.
m ³ /hour to precipitate (NH ₄ ) ₃ FeF ₆ crystals. In the apparatus of the present invention, almost no crystals were observed to adhere to the vessel walls or to accumulate or solidify at the bottom of the apparatus even after 24 days had passed since the start of operation. In addition, since the lower end of the downcomer pipe 8 is above the upper limit of the cooling zone 10, less organic solvent is incorporated into the crystal slurry, and as a result of analysis, the P content of the crystals is 0.31~
It was 0.60%.

[Brief explanation of drawings]

第１図は従来装置の一例の線図的断面図、第２
図は本発明の金属剥離用晶析装置の線図的断面
図、第３図は第２図の―線での断面図であ
る。符号の説明１……晶析装置本体、２……金属
抽出有機溶媒、３……有機溶媒温度調節器、４…
…剥離液（水相）、５……剥離液加熱器、６……
混合槽、７……撹拌装置、８……下降管、９……
結晶成長ゾーン、１０……剥離液冷却ゾーン、１
１……冷却剥離液排出口、１２……有機溶媒静置
区域、１３……有機溶媒溢流せき、１４……有機
溶媒排出口、１５……冷却剥離液導入口、１６…
…冷却剥離液ポンプ、１７……剥離液熱交換器、
１８……剥離液強制循環ゾーン、１９……循環剥
離液排出口、２０……循環剥離液ポンプ、２１…
…剥離液吹き出しノズル、２２……結晶分離ゾー
ン、２３……剥離液溢流せき、２４……剥離液排
出口、２５……結晶排出管。 Figure 1 is a diagrammatic sectional view of an example of a conventional device;
The figure is a diagrammatic cross-sectional view of the crystallizer for metal peeling of the present invention, and FIG. 3 is a cross-sectional view taken along the - line in FIG. 2. Explanation of symbols 1...Crystallizer main body, 2...Metal extraction organic solvent, 3...Organic solvent temperature controller, 4...
...Removal liquid (aqueous phase), 5...Removal liquid heater, 6...
Mixing tank, 7... Stirring device, 8... Downcomer pipe, 9...
Crystal growth zone, 10...Removal liquid cooling zone, 1
1...Cooling stripping liquid outlet, 12...Organic solvent standing area, 13...Organic solvent overflow weir, 14...Organic solvent outlet, 15...Cooling stripping liquid inlet, 16...
...Cooled stripping liquid pump, 17... Stripping liquid heat exchanger,
18... Stripping liquid forced circulation zone, 19... Circulating stripping liquid outlet, 20... Circulating stripping liquid pump, 21...
...Removal liquid blowout nozzle, 22...Crystal separation zone, 23...Removal liquid overflow weir, 24...Removal liquid outlet, 25...Crystal discharge pipe.

Claims

[Claims]

1 In an inverted conical crystallizer for extracting metal ions and stripping (back-extracting) metal ions as fluorides or fluoride complexes by bringing them into mixed contact with an organic solvent containing a heated fluoride-based stripping solution. , a cooling zone provided at the bottom of the inverted conical device main body and connected to an external heat exchanger, and a cooling zone provided in this cooling zone, and a substantially tangential direction provided at the bottom of the cooling zone to cause a swirling flow in the stripping liquid. A forced circulation zone having at least one blowing nozzle oriented in a direction.