JPH02248327A - Production of manganese sulfate solution - Google Patents
Production of manganese sulfate solutionInfo
- Publication number
- JPH02248327A JPH02248327A JP6894789A JP6894789A JPH02248327A JP H02248327 A JPH02248327 A JP H02248327A JP 6894789 A JP6894789 A JP 6894789A JP 6894789 A JP6894789 A JP 6894789A JP H02248327 A JPH02248327 A JP H02248327A
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- gas
- concentration
- manganese sulfate
- ore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 66
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 56
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 56
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002002 slurry Substances 0.000 claims abstract description 97
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 43
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000011572 manganese Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 4
- 150000002697 manganese compounds Chemical class 0.000 claims description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 67
- 238000006243 chemical reaction Methods 0.000 description 36
- 238000010521 absorption reaction Methods 0.000 description 22
- 239000002245 particle Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910016978 MnOx Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000219492 Quercus Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940075933 dithionate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、硫酸マンガン溶液の製造方法に関し、より詳
しくは酸化マンガン鉱石をスラリ状にしてＳ０２含有ガ
スと反応させることにより、所望濃度に調整された硫酸
マンガン溶液を得ることのできる製造方法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing a manganese sulfate solution, and more specifically, the present invention relates to a method for producing a manganese sulfate solution, and more specifically, the slurry of manganese oxide ore is adjusted to a desired concentration by reacting it with a S02-containing gas. The present invention relates to a manufacturing method capable of obtaining a manganese sulfate solution.
（従来の技術）
工業的な硫酸マンガン溶液の製造は、安価で入手の容易
なＭｎＯ，を主成分とする酸化マンガン鉱石（パイロル
ース鉱など）あるいはＭｎＣ０，を主成分とする炭酸マ
ンガン鉱石（菱マンガン鉱など）を原料とする方法が一
般的である。(Prior art) Industrial manganese sulfate solutions are manufactured using manganese oxide ores (such as pyroluthite) whose main component is MnO, which is cheap and easy to obtain, or manganese carbonate ore (rhodomanganese, etc.) whose main component is MnC0. The most common method is to use minerals (e.g., ore) as raw materials.
酸化マンガン鉱石を原料とする場合、ＭｎＯ，はそのま
までは硫酸と反応しないため、−旦ＭｎＧに還元焙焼し
てから硫酸と反応させて硫酸マンガンを得るか、あるい
は還元剤（デンプン、糖蜜など）の存在下に鉱石を硫酸
とを加熱反応させて、硫酸マンガンを得ている。When manganese oxide ore is used as a raw material, MnO does not react with sulfuric acid as it is, so it must first be reduced and roasted to MnG and then reacted with sulfuric acid to obtain manganese sulfate, or a reducing agent (starch, molasses, etc.) Manganese sulfate is obtained by heating the ore with sulfuric acid in the presence of .
前者の方法では、鉱石を粉砕し、通常はロータリーキル
ンなどで約１１００°Ｃ以上の高温で還元焙焼する。得
られたＭｎＯは塩基性で容易に硫酸と反応し、硫酸マン
ガン溶液が得られる。しかし、この方法は、焙焼のため
の設備や多量の熱エネルギーが必要であり、また２工程
を要するので操作が複雑になる。In the former method, the ore is crushed and then reduced and roasted at a high temperature of about 1100° C. or higher, usually in a rotary kiln or the like. The obtained MnO is basic and easily reacts with sulfuric acid to obtain a manganese sulfate solution. However, this method requires equipment for roasting and a large amount of thermal energy, and requires two steps, making the operation complicated.
後者の還元剤を用いる方法も、加熱反応であるので、加
熱に要するエネルギーおよび還元剤のコストが必要な上
、反応生成物の硫酸マンガンと還元剤との分離に煩雑な
操作が必要である。The latter method using a reducing agent also involves a heating reaction, which requires energy for heating and cost for the reducing agent, and requires complicated operations to separate the reaction product manganese sulfate from the reducing agent.
（発明が解決しようとする課ａ）
本発明の目的は、安価な酸化マンガン鉱石を原料として
、簡便な工程により硫酸マンガン溶液を経済的に製造す
ることのできる方法を提供することである。(Problem A to be Solved by the Invention) An object of the present invention is to provide a method for economically producing a manganese sulfate solution using a simple process using inexpensive manganese oxide ore as a raw material.
本発明の別の目的は、所望の任意の濃度に調整された硫
酸マンガン溶液を得ることのできる製造方法を提供する
ことである。Another object of the present invention is to provide a manufacturing method capable of obtaining a manganese sulfate solution adjusted to any desired concentration.
（課題を解決するための手段）
本発明者らは、酸化マンガン鉱石をスラリ状にしてＳＯ
！と反応させることにより、硫酸マンガンを容易に酸化
マンガン鉱石から直接製造することができ、上記目的が
達成されることを見出し、本発明を完成させた。(Means for solving the problem) The present inventors made manganese oxide ore into a slurry and SO
! The present inventors have discovered that manganese sulfate can be easily produced directly from manganese oxide ore by reacting with manganese oxide ore, and the above object can be achieved, and the present invention has been completed.
ここに、本発明の要旨は、酸化マンガン鉱石を含有する
原料スラリと１〜３０ ｖｏｌ％のＳＯ□を含有するガ
スとを多段式気泡塔内で接触させ、得られた回収スラリ
を固液分離することからなる、硫酸マンガン溶液の製造
方法である。Here, the gist of the present invention is to bring a raw material slurry containing manganese oxide ore into contact with a gas containing 1 to 30 vol% SO This is a method for producing a manganese sulfate solution.
より広義には、本発明は、酸化マンガン鉱石を含有する
原料スラリを、Ｓ低含有ガスと反応させ、得られた回収
スラリを固液分離することからなる、硫酸マンガン溶液
の製造方法である。More broadly, the present invention is a method for producing a manganese sulfate solution, which comprises reacting a raw material slurry containing manganese oxide ore with a low-S content gas and separating the obtained recovered slurry into solid and liquid.
（作用）
本発明の硫酸マンガンの製造方法は、次式で示さ、れる
周知の反応を利用したものである。(Function) The method for producing manganese sulfate of the present invention utilizes the well-known reaction represented by the following formula.
Ｍｎ０１ ＋ Ｓ０１ １ＭｎＳＯ４・・” ■
従来、この反応は、例えば、固体の二酸化マンガン微粉
末の層にＳＯ，含有ガスを通してガスの脱硫を行うとい
った乾式反応として主に利用されており、酸化マンガン
鉱石のスラリーに８０８含有ガスを接触させるという湿
式反応には利用されていなかった。Mn01 + S01 1MnSO4...” ■
Conventionally, this reaction has been mainly used as a dry reaction, for example, by passing SO and a gas containing gas through a layer of solid manganese dioxide fine powder to desulfurize the gas, and by bringing an 808-containing gas into contact with a slurry of manganese oxide ore. It has not been used for wet reactions.
しかし、本発明者らが検討した結果、気−液固相の接触
効率のよい反応装置を利用すれば、上記反応を湿式で効
率よ〈実施できることが判明した。また、その際に、反
応条件、特に各種成分の量的比率を適当に調整すること
により、得られる硫酸マンガン溶液の濃度を任意に調整
することができることも判明した。However, as a result of studies conducted by the present inventors, it has been found that the above reaction can be carried out efficiently in a wet manner by using a reaction apparatus with good gas-liquid solid phase contact efficiency. It has also been found that the concentration of the resulting manganese sulfate solution can be adjusted as desired by appropriately adjusting the reaction conditions, particularly the quantitative ratios of various components.
本発明の方法で使用する原料は、Ｍｎ０ｚを主成分とす
る酸化マンガン鉱石であり、その代表例はパイロルース
鉱（軟マンガン鉱）である、第１表にパイロルース鉱の
化学組成の例を示す。The raw material used in the method of the present invention is a manganese oxide ore containing MnOz as a main component, and a typical example thereof is pyroluthite (soft manganese ore). Table 1 shows an example of the chemical composition of pyroluthite.
第１表 （重量％）
使用鉱石の粒度は、スラリ形成可能な粒度であれば特に
制限されないが、細粒であるほど５０ｗガスとの接触面
積が大きく、反応性が高くなるため、最大粒径０．３−
以下とすることが好ましい。ただし、粒度が小さすぎる
と、経済性、作業環境面、装置閉塞等の観点で不都合を
生ずる恐れもある。Table 1 (% by weight) The particle size of the ore used is not particularly limited as long as it can form a slurry, but the finer the particle, the larger the contact area with the 50W gas and the higher the reactivity, so the maximum particle size 0.3-
The following is preferable. However, if the particle size is too small, there is a risk that disadvantages may arise from the viewpoints of economy, working environment, equipment clogging, etc.
鉱石の特に好ましい粒度範囲は、平均粒径で２０〜５０
ｍである。A particularly preferred particle size range of the ore is an average particle size of 20 to 50
It is m.
粒度調整した酸化マンガン鉱石を水と混合して、スラリ
を形成する。The sized manganese oxide ore is mixed with water to form a slurry.
スラリ中の原料鉱石の濃度は４０重量％以下とすること
が好ましい、鉱石中のＭｎＯ２が本発明の方法で完全に
ＭｎＳＯ４に転化されたと仮定すると、得られる硫酸マ
ンガン溶液中のＭｎ濃度は、原料スラリ中の鉱石濃度を
Ａ（重量％）、鉱石中のＭｎｏｚｉ１１度をＢ（重量％
）として、次式で算出できる。The concentration of raw material ore in the slurry is preferably 40% by weight or less. Assuming that MnO2 in the ore is completely converted to MnSO4 by the method of the present invention, the Mn concentration in the resulting manganese sulfate solution is The ore concentration in the slurry is A (weight%), and the Mnozi 11 degree in the ore is B (weight%).
), it can be calculated using the following formula.
１０００Ｘ （Ａ／１００） Ｘ （Ｂ／１００） Ｘ
（５５／８７） ＝Ｍｎ濃度（ｇ／ ｌ ）すなわち
、鉱石濃度Ａを上げると得られる硫酸マンガン溶液のＭ
ｎ濃度も上昇することになるが、実際の反応での実測値
は、第３図のグラフに実線で示すように、鉱石濃度が高
くなるほど計算値（破線）との差が大きくなる。このた
めＭｎＯ，−＋Ｍｎ５Ｏ。1000X (A/100) X (B/100) X
(55/87) = Mn concentration (g/l), that is, M of the manganese sulfate solution obtained by increasing the ore concentration A
Although the n concentration also increases, the difference between the measured value in the actual reaction and the calculated value (broken line) increases as the ore concentration increases, as shown by the solid line in the graph of FIG. Therefore, MnO, -+Mn5O.
の転化率が減少して、回収スラリ中の未反応鉱石量が増
加する。また、原料スラリ中の鉱石濃度が高すぎると操
作性も悪いため、上記の如く、スラリ中の鉱石濃度を４
０重量％以下、特に２０〜３０重量％とすることが好ま
しい。The conversion rate of is reduced and the amount of unreacted ore in the recovered slurry increases. In addition, if the ore concentration in the raw material slurry is too high, the operability will be poor, so as mentioned above, the ore concentration in the slurry should be increased to 4.
It is preferably 0% by weight or less, particularly 20 to 30% by weight.
原料鉱石スラリは、硫酸マンガンなどの水溶性マンガン
化合物を含有していてもよい。これにより、液中のＭｒ
＋イオン濃度が高くなるので、回収された硫酸マンガン
溶液のＭｎｌＪ度を上昇させることができる （第５図
参照）、シかし、液中にＭｎイオンが共存すると、Ｍｎ
０ｚとＳＯ意との反応が阻害されるため、液中の溶解Ｍ
ｎイオン濃度が高いほど供給したガス中のＳＯ２の吸収
率が低下する傾向がある（第４図参照）、ただし、第４
図に示すように、このＳＯχ吸収率の低下は、原料鉱石
の供給量を増大させることで補償することができ、例え
ば、原料鉱石スラリ中に８０ｇ／ ｌの溶解Ｍｎが共存
していても、門口６量を増加させることでＳＯｔを１０
０％吸収することは可能である。したがって、原料鉱石
スラリには１００ｇ／ｊ！程度までの液中Ｍｎ濃度が許
容される。The raw ore slurry may contain a water-soluble manganese compound such as manganese sulfate. As a result, Mr in the liquid
Since the + ion concentration increases, the MnlJ degree of the recovered manganese sulfate solution can be increased (see Figure 5). However, when Mn ions coexist in the solution, the Mn
Since the reaction between 0z and SO is inhibited, the dissolved M in the liquid
There is a tendency that the higher the n ion concentration, the lower the absorption rate of SO2 in the supplied gas (see Figure 4).
As shown in the figure, this decrease in the SOχ absorption rate can be compensated for by increasing the feed rate of raw ore; for example, even if 80 g/l of dissolved Mn coexists in the raw ore slurry, SOt by 10 by increasing the amount of gate 6
It is possible to absorb 0%. Therefore, the raw ore slurry contains 100 g/j! A concentration of Mn in the liquid up to a certain extent is acceptable.
また、この原料鉱石スラリは遊離の硫酸を含有していて
もよく、それによりＳＯ！吸収率および回収された硫酸
マンガン溶液のＭｎｌｌｌ度が高くなる。This raw ore slurry may also contain free sulfuric acid, thereby allowing SO! The absorption rate and the Mnllll degree of the recovered manganese sulfate solution are increased.
この目的には、硫酸を水中濃度が０．１〜３Ｎとなるよ
うな量で原料スラリに添加することが好ましい。３Ｎよ
り多量に添加すると反応に悪影響があり、Ｏ，１Ｎより
少ないと充分な効果が得られない。For this purpose, it is preferable to add sulfuric acid to the raw slurry in an amount such that the concentration in water is 0.1 to 3N. Adding more than 3N will have an adverse effect on the reaction, while adding less than 1N will not produce a sufficient effect.
本発明により酸化マンガン鉱石スラリと反応させるＳＯ
え含有ガスは、１〜３０ ｖｏｌ％のＳＯ□を含有する
任意のガスがよい、ガス中のＳ（ｈ含有量が１νｏ１％
より少ないと、反応に時間がかかり経済的でない＊ ３
０ ｖｏｌ％を超えると、Ｍｎ５ＯｓにＳＯ，かさらに
反応してジチオン酸塩（ＭｎＳ１０．）を生成する傾向
が出てくる。１〜３０ ｖｏｌ％のＳＯ８を含有するガ
スとしては、各種プロセスから得られるＳＯ□含有排ガ
スを利用することが経済的に有利である。このような排
ガスの例は、例えば、硫酸製造プラントの排ガス、硫酸
塩（例、硫酸マンガン）の焙焼工程における排ガスなど
である。必要であれば、ガス中のＳＯ□濃度を、空気な
どの適当なガスによる希釈あるいはより高濃度のＳＯ！
含有ガスとの混合により調整する。ガスの温度が高い場
合には、反応前に１００°Ｃより低温に、特に５０″Ｃ
より低温に冷却することが好ましい（前記０式の反応が
発熱反応であるので）。SO reacted with manganese oxide ore slurry according to the present invention
The gas containing S is preferably any gas containing 1 to 30 vol% SO□.
If the amount is less, the reaction takes longer and is not economical*3
If it exceeds 0 vol%, there is a tendency for Mn5Os to react with SO or further to produce dithionate (MnS10.). As the gas containing 1 to 30 vol% SO8, it is economically advantageous to use SO□-containing exhaust gas obtained from various processes. Examples of such exhaust gas include exhaust gas from a sulfuric acid manufacturing plant, exhaust gas from a process of roasting sulfates (eg, manganese sulfate), and the like. If necessary, the SO□ concentration in the gas may be diluted with a suitable gas such as air or a higher concentration of SO□ may be added.
Adjust by mixing with contained gas. If the gas temperature is high, lower than 100°C, especially 50"C, before the reaction.
It is preferable to cool to a lower temperature (because the reaction of equation 0 above is an exothermic reaction).
なお、ＳＯ１含有ガスとして各種排ガスを使用する場合
、ＳＯ□のほかにＳＯＷを含有するＳＯ，含有排ガスで
よい。この場合、排ガス中のＳＯｌは水中に溶解してＨ
ｚＳＯ＜ となり、これが酸化マンガン鉱石中に含まれ
るＭｎＯと反応して、次の反応式によりやはり硫酸マン
ガンが生成する。In addition, when using various exhaust gases as the SO1-containing gas, SO and containing exhaust gases containing SOW in addition to SO□ may be used. In this case, SOl in the exhaust gas is dissolved in water and H
zSO<, and this reacts with MnO contained in the manganese oxide ore to produce manganese sulfate according to the following reaction formula.
ＭｎＯ＋ ＨｚＳＯ＜→Ｍｎ５Ｏ，＋ ＨｌＯ・・−■
本発明の方法では、原料スラリとＳＯよ含有ガスとの接
触を多段式気泡塔で行うことが好ましい。MnO+ HzSO＜→Mn5O,+ HlO・・−■
In the method of the present invention, it is preferable that the raw material slurry and the SO-containing gas be brought into contact with each other in a multistage bubble column.
気泡塔は、気液接触装置の原型である攪拌槽に比べて構
造が簡単である上、゛気液接触面積が比較的大きく、ま
た多段式とすることにより、気泡塔の難点であった塔内
での液の混合・均一化が抑制されるので、塔底から比較
的高濃度の硫酸マンガンが溶解したスラリを回収するこ
とができる。Bubble columns have a simpler structure than the stirred tank, which is the prototype of gas-liquid contact equipment, and have a relatively large gas-liquid contact area.The bubble column also has a multi-stage design, which eliminates the drawbacks of bubble columns. Since mixing and homogenization of the liquid within the tower is suppressed, slurry in which relatively high concentration of manganese sulfate is dissolved can be recovered from the bottom of the tower.
１段式気泡塔では充分な接触に液深を多くとる必要があ
るので装置が大きくなる上、塔内の液が均一化されるの
で、高濃度の硫酸マンガン溶液を得にくい。充填塔は、
接触は充分であるが、運転時間の経過につれてスラリ中
の固形物が閉塞し、圧損が上昇するので、やがて運転不
能となる恐れが大である。単なる攪拌槽では接触が不十
分で、多数の楢を併置する必要がある。In a one-stage bubble column, it is necessary to increase the depth of the liquid for sufficient contact, which increases the size of the apparatus, and because the liquid in the column is homogenized, it is difficult to obtain a highly concentrated manganese sulfate solution. The packed tower is
Although the contact is sufficient, as the operating time elapses, the solids in the slurry become clogged and the pressure drop increases, so there is a great possibility that the system will eventually become inoperable. A simple stirring tank does not provide sufficient contact, so it is necessary to place many oaks side by side.
多段式気泡塔の仕切部（通常は多孔板製）の開孔率（仕
切部ガス通過断面積の塔内ガス通過断面積に対する割合
）は１〜４０％とすることが好ましい、これより開孔率
が小さいと、背圧が大きく、ガスの供給や液の流下が困
難となる。開孔率が４０％を超えると、多段式気泡塔の
利点が失われる。It is preferable that the porosity of the partitions (usually made of perforated plates) of the multistage bubble column (the ratio of the gas passage cross-sectional area of the partition to the gas passage cross-section area in the column) is 1 to 40%. If the ratio is small, the back pressure will be large and it will be difficult to supply gas and flow down the liquid. When the porosity exceeds 40%, the advantages of the multistage bubble column are lost.
ガスとスラリとの供給比は鉱石スラリ中のＭｎ０ｔとガ
ス中のＳｏｌとのモル比（以下、Ｈｎ０１／ＳＯ，モル
比という）が適正値になるように調整する。ここで、Ｍ
ｎ０ｇ／Ｓｏｗモル比とは、単位時間当たり反応装置に
供給された原料スラリ中の１Ｉｌｎｏｔモル数とＳＯ□
含有ガス中のＳＯｘモル数との比を意味する。原料スラ
リ中の鉱石濃度が一定の場合、このＭｎ０ｚ／ＳＯ□モ
ル比が大きいほどＳｏｌ吸収率が高くなり、液中の溶解
Ｍｎ濃度は減少する。The supply ratio of gas and slurry is adjusted so that the molar ratio of Mn0t in the ore slurry to Sol in the gas (hereinafter referred to as Hn01/SO, molar ratio) is an appropriate value. Here, M
The n0g/Sow molar ratio refers to the number of moles of 1Ilnot in the raw material slurry supplied to the reactor per unit time and the number of moles of SO□
It means the ratio to the number of moles of SOx in the contained gas. When the ore concentration in the raw material slurry is constant, the larger the Mn0z/SO□ molar ratio, the higher the Sol absorption rate and the lower the dissolved Mn concentration in the liquid.
第４図および第５図に、原料スラリ中のＭｎ濃度が０お
よび８０ｇ／ ｌの場合について、Ｍｎ０ｘ１５０□モ
ル比とＳ（ｈ吸収率および回収溶液中Ｍｎ濃度の関係を
それぞれ示す、試験は、多孔板９段を備えた気泡塔を用
いて、ガス空塔速度１５ ｃｍ ／ ｓ、ガス中ＳＯ，
濃度５ ｖｏｌ％、原料スラリ中鉱石濃度２０ｗｔ％の
条件で行りた。原料スラリか溶解マンガンを含有しない
Ｏ１ｎ濃度Ｏｇ／ １ ）場合、上記モル比がｌでＳＯ
！が完全に吸収されるはずであるが、実際にはモル比０
．８．程度でＳＯ，は完全に吸収され、気泡塔の出口で
ＳＯｘは検出されなかった。これは、鉱石中に存在する
金属不純物（ＡＩ＋ Ｋ＋ Ｆｅなと）もＳＯ□と反応
するためである。Figures 4 and 5 show the relationship between the Mn0x150□ molar ratio, the S(h absorption rate, and the Mn concentration in the recovered solution) when the Mn concentration in the raw material slurry was 0 and 80 g/l, respectively. Using a bubble column with 9 stages of perforated plates, superficial gas velocity 15 cm/s, SO in gas,
The test was carried out under the conditions that the concentration was 5 vol% and the ore concentration in the raw material slurry was 20 wt%. When the raw material slurry does not contain dissolved manganese and has an O1n concentration of Og/1), the above molar ratio is l and SO
! should be completely absorbed, but in reality the molar ratio is 0.
．． 8. SOx was completely absorbed at the outlet of the bubble column, and no SOx was detected at the outlet of the bubble column. This is because metal impurities (such as AI+K+Fe) present in the ore also react with SO□.
第４図および第５図から、Ｍｎ０ｔ／ＳＯｘモル比が大
きいほどＳＯｘ吸収率が高くなり、液中の溶解Ｍｎｆｉ
度は減少する１頃向があることがわかる＊ Ｍｎ０ｚ／
ＳＯ□モル比は０．６以上とすることが好ましい、この
モル比が０．６より小さいと、ＳＯ３回収率が悪化する
。From Figures 4 and 5, the larger the Mn0t/SOx molar ratio, the higher the SOx absorption rate, and the dissolved Mnfi in the liquid
It can be seen that the degree decreases around 1* Mn0z/
The SO□ molar ratio is preferably 0.6 or more; if this molar ratio is smaller than 0.6, the SO3 recovery rate will deteriorate.
モル比の上限は特に限定されないが、高くしすぎると未
反応の鉱石が増大するので、Ｓ０２吸収率との兼ね合い
で適当なモル比に設定する。The upper limit of the molar ratio is not particularly limited, but if it is too high, the amount of unreacted ore increases, so the molar ratio is set to an appropriate value in consideration of the S02 absorption rate.
なお、原料スラリ中に遊離硫酸が存在する場合には、硫
酸も鉱石と反応するため、硫酸を含有しない場合に比べ
て、同じＳＯｘ吸収率を得るのに、門１０□／Ｓ０８モ
ル比を高くする必要が一般にある。In addition, if free sulfuric acid is present in the raw material slurry, sulfuric acid also reacts with the ore, so the molar ratio of 10□/S08 must be set higher to obtain the same SOx absorption rate than when no sulfuric acid is contained. There is generally a need to do so.
反応温度は特に制限されず、周囲温度から反応液の沸点
までの任意の温度で行うことができるが、好ましい反応
温度は５０〜８０℃である。The reaction temperature is not particularly limited and can be carried out at any temperature from ambient temperature to the boiling point of the reaction solution, but the preferred reaction temperature is 50 to 80°C.
本発明の方法は、例えば第１図に示す要領で実施するこ
とができる。必要に応じてＭｎＳＯ４などの水溶性マン
ガン化合物および硫酸を添加して組成を調整した酸化マ
ンガン鉱石の原料スラリは、貯槽ｌからポンプ等により
多段式気泡塔２の上部に供給する。貯槽１内の原料スラ
リは常時攪拌しておくことが好ましい、Ｓ０３含有ガス
をブロワ（図示せず）で吸引して気泡塔の塔底に送給し
、気泡塔内のスラリと接触させると、スラリ中のＭｎＯ
業とガス中のＳ（ｈとが反応してＭｎ５Ｏａが生成する
。こうしてＳ０８が除去されたガスは気泡塔上部より排
出される。Ｓ０８吸収率が１００％である場合には、排
ガスはそのまま大気中へ放散できるが、ＳＯ，が残留し
ている場合には、アルカリ中和などの適宜の脱硫装置に
より無害化してから放散する。気泡塔の塔底からは、Ｍ
ｎ５Ｏ，を含有する回収スラリを抜き取る。抜き出され
た回収スラリを、濾過機、遠心分離機、沈降槽などの適
当な固液分離装置３で固液分離して未反応の鉱石あるい
は鉱石中の不溶性不純物（脈石）を除去すると、硫酸マ
ンガン溶液が得られる。この硫酸マンガン溶液には、鉱
石中に存在していたＡＱ、 Ｆｅ、 Ｋなどの金属の化
合物も少量溶解しているので、必要であれば、この硫酸
マンガン溶液を常法（例、沈殿形成）により精製する。The method of the present invention can be carried out, for example, as shown in FIG. A raw material slurry of manganese oxide ore, the composition of which has been adjusted by adding a water-soluble manganese compound such as MnSO4 and sulfuric acid as necessary, is supplied from the storage tank 1 to the upper part of the multistage bubble column 2 by a pump or the like. It is preferable to constantly stir the raw material slurry in the storage tank 1. When the S03-containing gas is sucked by a blower (not shown) and fed to the bottom of the bubble column and brought into contact with the slurry in the bubble column, MnO in slurry
Mn5Oa is produced by the reaction between S08 and S(h) in the gas.The gas from which S08 has been removed is discharged from the upper part of the bubble column.If the S08 absorption rate is 100%, the exhaust gas is directly released into the atmosphere. However, if SO remains, it should be rendered harmless by an appropriate desulfurization device such as alkali neutralization, and then released.
The recovered slurry containing n5O is withdrawn. The extracted recovered slurry is solid-liquid separated by a suitable solid-liquid separator 3 such as a filter, centrifuge, or sedimentation tank to remove unreacted ore or insoluble impurities (gangue) in the ore. A manganese sulfate solution is obtained. This manganese sulfate solution also dissolves a small amount of metal compounds such as AQ, Fe, and K that were present in the ore. Purify by
また、晶析により硫酸マンガンの結晶を取得することも
できる。Moreover, crystals of manganese sulfate can also be obtained by crystallization.
なお、図示例にあっては、ガスとスラリは向流接触であ
るが、スラリを気泡塔下部から供給する並流方式、ある
いは回収スラリを気泡塔に再度供給する循環方式なども
可能である。In the illustrated example, the gas and the slurry are in countercurrent contact, but a parallel flow system in which the slurry is supplied from the lower part of the bubble column, or a circulation system in which the recovered slurry is supplied again to the bubble column, etc., are also possible.
以上に説明したように、本発明の方法によれば、１１ｎ
Ｏ，／ＳＯ，モル比、ならびに鉱石スラリ中の鉱石濃度
、溶解Ｍｎ濃度、遊離硫酸濃度を調整することにより、
得られる硫酸マンガン溶液の？Ｉｎ濃度を所望の値とす
ることができる。As explained above, according to the method of the present invention, 11n
By adjusting the O, /SO, molar ratio, ore concentration, dissolved Mn concentration, and free sulfuric acid concentration in the ore slurry,
of manganese sulfate solution obtained? The In concentration can be set to a desired value.
例えば、回収される硫酸マンガン溶液中のＭｎｆｉ度を
高くするには、高濃度の溶解Ｍｎを含有させた原料鉱石
スラリを用いることが有利である。また、ＭｎＯｘ／Ｓ
０ｗモル比を小さくすると、回収溶液中のＭｎ濃度が高
く、かつ原料鉱石の反応率が向上し、未反応鉱石が少な
くなる。しかし、このような条件下では、ＳＯ□吸収率
が１００％に達しないことがあリ、その場合には排ガス
をそのまま系外へ放出することはできないため、排ガス
の脱硫処理が必要となる。このような低濃度のＳＯ８の
脱硫処理は、一般にはアルカリ類での中和により行なわ
れるが、ランニングコストがかかるだけでなく、製造原
料であるＳＯ２ガスを捨てることになり、経済的でない
、また、Ｓｏｗを完全に吸収したい場合には、原料スラ
リの液中Ｍｎ１１１度を低くし、Ｍｎ０ｔ／Ｓｏ□モル
比を大きくすることが必要となり、高ＭｒｉｌＩ度の硫
酸マンガン溶液を得ることは困難となる。For example, in order to increase the Mnfi degree in the recovered manganese sulfate solution, it is advantageous to use a raw material ore slurry containing a high concentration of dissolved Mn. Also, MnOx/S
When the 0w molar ratio is decreased, the Mn concentration in the recovered solution is high, the reaction rate of the raw ore is improved, and the amount of unreacted ore is reduced. However, under such conditions, the SO□ absorption rate may not reach 100%, and in that case, the exhaust gas cannot be directly discharged to the outside of the system, so the exhaust gas needs to be desulfurized. Desulfurization treatment for such low-concentration SO8 is generally performed by neutralizing with alkali, but this not only increases running costs but also wastes SO2 gas, which is the raw material for production, making it uneconomical and If you want to completely absorb Sow, it is necessary to lower the Mn111 degree in the liquid of the raw material slurry and increase the Mn0t/So□ molar ratio, making it difficult to obtain a manganese sulfate solution with a high Mril degree. .
本発明の好適態様においては、２以上の気泡塔を設けて
、原料スラリと５０ｗ含有ガスとの反応を多段操作で行
う、この場合、２段目移行の反応塔でｔまアルカリ処理
の代替としてガスの脱硫が行われる０通常は２塔の気泡
塔を設けることで、排ガス中のｓｏ、 １度がＯとなり
、そのまま大気に放散することができる。In a preferred embodiment of the present invention, two or more bubble columns are provided, and the reaction between the raw material slurry and the 50W-containing gas is carried out in a multi-stage operation. Usually, two bubble columns are installed to desulfurize the gas, so that 1°C in the exhaust gas becomes O, which can be released directly into the atmosphere.
気泡塔を２基設けた場合の工程の概略を第２図に示す、
原料スラリ４を第二気泡塔５に供給し、この塔内で第一
気泡塔を通過したＳＯ１含有ガスと向流接触させる。第
二気泡塔の目的は、ガス中のＳＯｘの完全な吸収である
ので、第二気泡塔に供給する原料スラリは溶解Ｍｎ濃度
を低くし、ＭＩＩＯ！１５０１モル比を高くする。原料
スラリ中の溶解Ｍｎ濃度をＯｇ／ ｌ （ＭｎＳＯ４無
添加）とし、Ｍｎ０ｚ／Ｓｏｙモル比を０．８以上、特
に１．０以上とすることが好ましい。Figure 2 shows an outline of the process when two bubble columns are installed.
The raw material slurry 4 is supplied to the second bubble column 5, where it is brought into countercurrent contact with the SO1-containing gas that has passed through the first bubble column. The purpose of the second bubble column is to completely absorb SOx in the gas, so the raw material slurry fed to the second bubble column has a low dissolved Mn concentration and MIIO! 1501 Increase the molar ratio. It is preferable that the dissolved Mn concentration in the raw material slurry is Og/l (without addition of MnSO4), and the Mn0z/Soy molar ratio is 0.8 or more, particularly 1.0 or more.
この原料スラリの鉱石濃度は２０〜３０％が好ましく、
また！酸を０．１〜３Ｎの範囲内でスラリに添加しても
よい。The ore concentration of this raw material slurry is preferably 20 to 30%,
Also! Acid may be added to the slurry in the range of 0.1-3N.
第二気泡塔の塔底から抜き出された中間スラリ６は、Ｍ
ｎＯよ７８０２モル比および鉱石濃度などの第二気泡塔
での反応条件に応じた液中Ｍｎ濃度を有するが、原料ス
ラリの溶解Ｍｎ濃度が低いので、液中Ｍｎ濃度は、例え
ば６０〜１００ｇ＃！の範囲と比較的低い。The intermediate slurry 6 extracted from the bottom of the second bubble column is M
The Mn concentration in the liquid depends on the reaction conditions in the second bubble column, such as the nO7802 molar ratio and ore concentration, but since the dissolved Mn concentration in the raw material slurry is low, the Mn concentration in the liquid is, for example, 60 to 100 g#. ! range and relatively low.
また、ＭｎＯ，／ＳＯ□モル比が高いので、通常は未反
応のＭＩＩＯ！を含有している。Also, since the MnO,/SO□ molar ratio is high, unreacted MIIO! Contains.
この中間スラリを第一気泡塔７においてＳＯ１含有ガス
と向流接触させる。第一気泡塔では、ＳＯｘの完全な吸
収は必要ないので、所望のＭｎ濃度の硫酸マンガン溶液
が得られるように反応条件を設定することができる０例
えば、中間スラリには、第一気泡塔でのＭｎＯ□／ＳＯ
８モル比の設定値に不足する鉱石および／または水（場
合により硫酸も）を加えることができ、また、第一気泡
塔で高濃度のＭｎを含有する硫酸マンガン溶液を生成し
たい場合には、不足する溶解Ｍｌｌ （ＭＩＩＳＯ４）
を加えることもできる。したがって、中間スラリに添加
する水の一部もしくは全部として、例えば、回収された
硫酸マンガンの晶析時に得られた母液などの高濃度の硫
酸マンガン溶液も使用できる。This intermediate slurry is brought into countercurrent contact with the SO1-containing gas in the first bubble column 7. In the first bubble column, complete absorption of SOx is not required, so the reaction conditions can be set so as to obtain a manganese sulfate solution with the desired Mn concentration. MnO□/SO
The missing ore and/or water (and optionally sulfuric acid) can be added to the set value of the 8 molar ratio, and if it is desired to produce a manganese sulfate solution containing a high concentration of Mn in the first bubble column, Missing dissolved Mll (MIISO4)
You can also add Therefore, a highly concentrated manganese sulfate solution, such as a mother liquor obtained during crystallization of recovered manganese sulfate, can also be used as part or all of the water added to the intermediate slurry.
第一気泡塔では、例えば１００〜１８０ｇ＃！という高
いＭｎ１度の硫酸マンガン溶液を得ることができる。ま
た、ＭｎＯ，／Ｓｏｔモル比を０．６〜０．８と小さく
し、スラリ濃度も小さくすることで、未反応鉱石量を最
小にすることができる。In the first bubble column, for example, 100 to 180 g#! A manganese sulfate solution with a high Mn content of 1 degree can be obtained. Further, by reducing the MnO,/Sot molar ratio to 0.6 to 0.8 and reducing the slurry concentration, the amount of unreacted ore can be minimized.
このようにＳＯ□ガスを第一気泡塔と第二気泡塔を順次
通過させることにより、第二気泡塔で完全にＳＯ３を吸
収させることが可能となり、その排ガスを大気に排出す
ることができると同時に、第一気泡塔で任意の所望濃度
のＭｎを溶液中に含有するスラリを回収することができ
る。By passing the SO□ gas sequentially through the first bubble column and the second bubble column, it is possible to completely absorb SO3 in the second bubble column, and the exhaust gas can be discharged into the atmosphere. At the same time, a slurry containing any desired concentration of Mn in solution can be recovered in the first bubble column.
第一気泡塔から回収されたスラリは、上記と同様に固液
分離すると、所望Ｍｎ濃度の硫酸マンガン溶液が得られ
る。The slurry recovered from the first bubble column is subjected to solid-liquid separation in the same manner as described above to obtain a manganese sulfate solution with a desired Mn concentration.
以下、実施例により本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
爽胤阻↓
本実施例は、第１図に示すように、気泡塔を１基設けた
装置による硫酸マンガン溶液の製造を例示する。This example illustrates the production of a manganese sulfate solution using an apparatus equipped with one bubble column, as shown in FIG.
使用した気泡塔は、直径３００ Ｍ、高さ３０００鵬の
多段式気泡塔であって、塔内に直径５閣の孔を１６舗ピ
ンチで３１３個設けた多孔板（開孔率８．７％）により
仕切られた高さ３００論の１ｌｌｌｌ’ｌを９段有して
いる。The bubble column used was a multi-stage bubble column with a diameter of 300 m and a height of 3000 m, and a perforated plate with 313 holes of 5 diameters in 16 holes (open area ratio 8.7%). ) It has nine stages of 1llll'l with a height of 300 degrees.
第１表に示す組成の酸化マンガン鉱石を粉砕して、平均
粒径２Ｂ、２．ＩＪｌ、最大粒径１０５−１最小粒径２
−とじたものを用いて、鉱石２４１％を含有する原料ス
ラリを調製した。原料スラリの調製は、この鉱石に水お
よび必要によりＭｎＳＯ４を所定量添加し、さらに濃硫
酸を液中濃度がＩＮとなる量で添加することにより行っ
た。Manganese oxide ore having the composition shown in Table 1 was crushed to obtain an average particle size of 2B, 2. IJl, maximum particle size 105-1 minimum particle size 2
- A raw material slurry containing 241% ore was prepared using the bound material. The raw material slurry was prepared by adding a predetermined amount of water and, if necessary, MnSO4 to this ore, and further adding concentrated sulfuric acid in an amount such that the concentration in the liquid was IN.
この原料スラリを、所定のＭｎＯ寥／ＳＯｘモル比とな
る速度で貯槽から上記気泡塔の上部に供給し、塔底から
は硫酸マンガンの焙焼炉で発生したｓｏ８含有排ガスを
、５Ｏ１濃度が５ ｖｏｌ％となるように空気で希釈し
、常温で供給することにより、ｓｏ、と原料スラリとの
反応行った。塔内のスラリの滞留時間は約７０分、ガス
空塔速度は１５ Ｃ１１／ Ｓであり、平均温度は約５
０℃であった。This raw material slurry is supplied from the storage tank to the upper part of the bubble column at a rate that achieves a predetermined MnO volume/SOx molar ratio, and from the bottom of the column, the SO8-containing exhaust gas generated in the manganese sulfate roasting furnace is The reaction between SO and the raw material slurry was carried out by diluting it with air to a volume of % and supplying it at room temperature. The residence time of the slurry in the column is about 70 minutes, the gas superficial velocity is 15 C11/S, and the average temperature is about 5
It was 0°C.
気泡塔の塔底からは、気液混相レベルが一定となる速度
で回収スラリを抜き出した０回収スラリは、タンクに集
め、反応終了後に濾過により固形物を分離除去して、硫
酸マンガン溶液を得た。この溶液の金属含有量をｌｌＭ
ｎ０．滴定法により測定した。また、気泡塔から出た排
ガスは、ｓｏオ濃度を測定し、必要によりアルカリ中和
してから放散させた。The recovered slurry was extracted from the bottom of the bubble column at a rate that kept the gas-liquid mixed phase level constant. The recovered slurry was collected in a tank, and after the reaction was completed, the solid matter was separated and removed by filtration to obtain a manganese sulfate solution. Ta. The metal content of this solution is 1M
n0. Measured by titration method. In addition, the exhaust gas discharged from the bubble column was measured for SO concentration, neutralized with alkali if necessary, and then released.
反応条件、回収スラリの溶液中の金属含有量、および排
ガス中のＳＯ，濃度およびｓｏ８吸収率を後出の第２表
にまとめて示す。The reaction conditions, the metal content in the recovered slurry solution, and the SO concentration and SO8 absorption rate in the exhaust gas are summarized in Table 2 below.
本実施例は、第２図に示すように２基の気泡塔を設けた
多段操作の例を示す、使用した２基の気泡塔は、いずれ
も実施例１と同じ仕様のものであった。This example shows an example of multi-stage operation using two bubble columns as shown in FIG. 2. Both of the two bubble columns used had the same specifications as in Example 1.
原料スラリは実施例１と同様である（鉱石濃度２０重量
％、硫酸濃度ＩＮ）が、Ｍｎ５Ｏ，は添加しなかった。The raw material slurry was the same as in Example 1 (ore concentration 20% by weight, sulfuric acid concentration IN), but Mn5O was not added.
このスラリを第二気泡塔に供給し、第一気泡塔から排出
されたＳｏｌ含有ガスと接触させた。This slurry was supplied to the second bubble column and contacted with the Sol-containing gas discharged from the first bubble column.
ガスの供給速度は、第二気泡塔で・のＭｎ０１ＩＳＯ，
モル比が所定値（１，０）になるように調整した。第二
気泡塔の塔底から抜き出された中間スラリは、これに粉
砕鉱石、水、ＭｎＳＯ４を加えてスラリ組成を調整した
後、第一気泡塔に供給し、ＳＯ２濃度を５．０または１
１．Ｏｖｏｌ％に調整した硫酸マンガン焙焼炉排ガスと
接触させた。第一および第二気泡塔でのガス空塔速度は
ともに１５ｃ−／３であり、スラリ滞留時間はそれぞれ
６０分および１００分であった。塔内の平均温度は、第
一気泡塔が６５°Ｃ１第二気泡塔が４０℃であった。第
一気泡塔から抜き出された回収スラリの溶液の組成およ
び第二気泡塔からの排ガス中のＳＯ□および全体のＳＯ
，Ｔ＆収率を、各気泡塔での反応条件と共に次の第２表
に併せて示す、なお、第２表において、反応条件の数値
は、上段の数値が第一気泡塔での条件、カッコ内の下段
の数値は第二気泡塔での条件を示す。The gas supply rate was Mn01ISO,
The molar ratio was adjusted to a predetermined value (1,0). The intermediate slurry extracted from the bottom of the second bubble column is mixed with crushed ore, water, and MnSO4 to adjust the slurry composition, and then supplied to the first bubble column to adjust the SO2 concentration to 5.0 or 1.
1. It was brought into contact with manganese sulfate roasting furnace exhaust gas adjusted to Ovol%. The gas superficial velocities in the first and second bubble columns were both 15c-/3, and the slurry residence times were 60 minutes and 100 minutes, respectively. The average temperature inside the column was 65° C. in the first bubble column and 40° C. in the second bubble column. Composition of the solution of the recovered slurry extracted from the first bubble column, SO□ in the exhaust gas from the second bubble column, and total SO
, T & yield are shown together with the reaction conditions in each bubble column in the following Table 2. In Table 2, the numerical values of the reaction conditions are shown in the upper column, the conditions in the first bubble column, The lower numbers in the figure indicate the conditions in the second bubble column.
第２表
（以下金白）
第２表かられかるように、気泡塔が１基の実施例１の場
合、ＭｎＯ□／Ｓｏ□モル比が１．０の条件では、原料
スラリが溶解Ｍｎを含有しなければ（試験Ａ）、ＳＯｌ
の吸収率は１００％となるが、回収スラリ中のＭｎ濃度
は６７ｇ／ ｊ！と低い、一方、試験Ｂのように、原料
スラリ中に可溶性Ｍｎ塩を含有させておくと、比較的高
いＭｎｆｉ度の硫酸マンガン溶液が得られるが、ＳＯ２
吸収率を１００％とすることができず、排ガスの処理が
余分に必要となる。Table 2 (hereinafter referred to as Kinpaku) As seen from Table 2, in the case of Example 1 with one bubble column, when the MnO□/So□ molar ratio is 1.0, the raw material slurry contains dissolved Mn. If it does not contain (Test A), SOl
The absorption rate is 100%, but the Mn concentration in the recovered slurry is 67 g/j! On the other hand, if a soluble Mn salt is included in the raw material slurry as in Test B, a manganese sulfate solution with a relatively high Mnfi degree can be obtained, but SO2
The absorption rate cannot be 100%, and extra treatment of the exhaust gas is required.
実施例２のように、気泡塔を２基設置すると、ＳＯ□吸
収率を１００％としながら、１５０ｇ／ｆを超える非常
に高濃度のＭｎを含有する硫酸マンガン溶液を得ること
ができた。実施例２の試ＭＢでは、１１％という高濃度
のＳＯｔを含有するガスを吸収させたが、１００％の８
０８吸収率を達成することができた。この場合、中間ス
ラリの溶解Ｍｎｆｉ度は７０ｇ／ １と試験Ａよりやや
低かったが、第一気泡塔に供給したＳＯ８濃度が高＜
、ＭｎＯｘ／ＳＯｘモル比が小さかったために、最終的
に回収された硫酸マンガン溶液のＭｎｆｉ度は１７９
ｇ／ｊ！と試験Ａの１６４ｇ／ｌより高くなったことが
注目される。すなわち、得られる硫酸マンガン溶液のＭ
ｎ濃度は、原料スラリ中のＭｎ濃度のみならず、Ｍｎ０
１／ＳＯ□モル比にも相当に依存するのである。When two bubble columns were installed as in Example 2, it was possible to obtain a manganese sulfate solution containing an extremely high concentration of Mn exceeding 150 g/f while keeping the SO□ absorption rate at 100%. In the sample MB of Example 2, a gas containing SOt at a high concentration of 11% was absorbed, but 100% of SOt was absorbed.
08 absorption rate could be achieved. In this case, the dissolved Mnfi degree of the intermediate slurry was 70 g/1, which was slightly lower than Test A, but the SO8 concentration supplied to the first bubble column was high.
, because the MnOx/SOx molar ratio was small, the Mnfi degree of the finally recovered manganese sulfate solution was 179.
g/j! It is noteworthy that this value was higher than that of Test A, which was 164 g/l. That is, M of the obtained manganese sulfate solution
The n concentration includes not only the Mn concentration in the raw material slurry but also the Mn0
It also depends considerably on the 1/SO□ molar ratio.
夫崖■工
実施例１の試験Ａと同様にして、気泡塔１基を用いた硫
酸マンガンの製造を行った０反応条件は、スラリ中鉱石
含有量２０重置％、ガス中ＳＯ，濃度５ｖｏｌ％、スラ
リ空塔速度１５ｃｍ／ｓ、 Ｍｎ０ｔ／ＳＯ，−Ｔ−７
Ｌ／比０．７であり、原料スラリにはＭｎ５Ｏ，を添加
せず、硫酸濃度を０〜３Ｎの範囲内で変動させた。Manganese sulfate was produced using one bubble column in the same manner as Test A of Example 1. The reaction conditions were: ore content in the slurry was 20% by weight, SO in the gas, and the concentration was 5 vol. %, slurry superficial velocity 15 cm/s, Mn0t/SO, -T-7
The L/ratio was 0.7, no Mn5O was added to the raw material slurry, and the sulfuric acid concentration was varied within the range of 0 to 3N.
反応成績を原料スラリ中の硫酸濃度と共に、次の第３表
に示す。The reaction results are shown in Table 3 below along with the sulfuric acid concentration in the raw material slurry.
第３表
本実施例では、ＳＯＷ吸収率への影響を調べるため、Ｍ
ｎ０１／ＳＯ，モル比を０．７と低くして、ＳＯ，吸収
率が１００％に達しない条件で反応を行った。原料スラ
リ中に硫酸を添加しないと、ＳＯ２吸収率は９６％で、
回収液中Ｍｎｆｉ度は７３ｇ／ １であったのに対し、
硫酸を添加すると、ＳＯ１吸収率は９９％まで向上させ
ることができ、またＭｎ１度も改善された。Table 3 In this example, in order to investigate the influence on the SOW absorption rate, M
The reaction was carried out under conditions where the n01/SO molar ratio was as low as 0.7 and the SO absorption rate did not reach 100%. If sulfuric acid is not added to the raw material slurry, the SO2 absorption rate is 96%,
The Mnfi degree in the recovered liquid was 73g/1,
When sulfuric acid was added, the SO1 absorption rate could be improved to 99%, and the Mn1 degree was also improved.
（発明の効果）
本発明の方法によれば、酸化マンガン鉱石のスラリを多
段式気泡塔においてＳＯよ含有ガスと反応させることに
より、Ｍｎ（ｌｚをＭｎＳＯ４に直接転化させることが
でき、ＳＯｔ含有ガスとしては各種の排ガスを利用でき
るため、従来の方法と比較して安価かつ簡便な操作で硫
酸マンガン溶液を得ることができる。(Effects of the Invention) According to the method of the present invention, Mn(lz) can be directly converted to MnSO4 by reacting a slurry of manganese oxide ore with SO-containing gas in a multistage bubble column, and SOt-containing gas can be directly converted into MnSO4. Since various exhaust gases can be used, a manganese sulfate solution can be obtained at a lower cost and with a simpler operation than conventional methods.
また、本発明の方法においては、反応条件を調整するこ
とにより、得られる硫酸マンガン溶液のＭｎｆｉ度を制
御できる。さらに、本発明の方法において、反応を多段
操作で行うことにより、ＳＯ，の吸収率１００％を維持
しながら、高−ｎｉ１１度の硫酸マンガン溶液を得るこ
とができ、排ガスをそのまま放散させることができる。Furthermore, in the method of the present invention, the Mnfi degree of the obtained manganese sulfate solution can be controlled by adjusting the reaction conditions. Furthermore, in the method of the present invention, by carrying out the reaction in multiple stages, it is possible to obtain a high-ni 11 degree manganese sulfate solution while maintaining a 100% absorption rate of SO, and it is possible to directly dissipate the exhaust gas. can.
従って、本発明の方法は、ＳＯ８含有排ガスを利用して
、硫酸マンガン溶液を製造すると同時に、排ガスを無害
化処理することができる点で、非常に有利な方法である
。Therefore, the method of the present invention is a very advantageous method in that it is possible to produce a manganese sulfate solution using SO8-containing exhaust gas and at the same time to detoxify the exhaust gas.
第１図は、気泡塔を１基使用した場合の本発明の方法の
略式説明図、
第２図は、気泡塔を２基使用した場合の本発明の方法の
略式説明図、
第３図は、原料スラリ中の鉱石濃度と得られる回収液中
のＭｎ濃度との関係を、Ｍｎ０１転化率１００％と仮定
した時の計算値と対比させて示すグラフ、第４図は、Ｍ
ｎ０１／ＳＯｘモル比とＳ６吸収率との関係を示すグラ
フ、および
第５図は、Ｍｎ０１／ＳＯｘモル比と回収液中Ｍｎ１Ｊ
度との関係を示すグラフである。FIG. 1 is a schematic illustration of the method of the present invention when one bubble column is used. FIG. 2 is a schematic illustration of the method of the invention when two bubble columns are used. , a graph showing the relationship between the ore concentration in the raw material slurry and the Mn concentration in the recovered liquid obtained, in comparison with the calculated value assuming an Mn01 conversion rate of 100%.
The graph showing the relationship between the n01/SOx molar ratio and the S6 absorption rate and FIG.
It is a graph showing the relationship with degree.
Claims (4)
３０ｖｏｌ％のＳＯ＿２を含有するガスとを、多段式気
泡塔内で接触させ、得られた回収スラリを固液分離する
ことからなる、硫酸マンガン溶液の製造方法。(1) Raw material slurry containing manganese oxide ore;
A method for producing a manganese sulfate solution, which comprises contacting a gas containing 30 vol% SO_2 in a multistage bubble column and separating the obtained recovered slurry into solid and liquid.
または遊離の硫酸を含有し、原料スラリ中のＭｎＯ＿２
とガス中のＳＯ＿２のモル比、ならびに原料スラリ中の
鉱石濃度、溶解Ｍｎイオン濃度および遊離硫酸濃度から
選ばれた１以上のパラメータの調整により、所望濃度の
硫酸マンガン溶液を得ることを特徴とする、請求項１記
載の方法。(2) The raw material slurry contains a water-soluble manganese compound and/or
or containing free sulfuric acid, MnO_2 in the raw slurry
The method is characterized in that a manganese sulfate solution with a desired concentration is obtained by adjusting one or more parameters selected from the molar ratio of SO_2 and SO_2 in the raw material slurry, the ore concentration in the raw material slurry, the dissolved Mn ion concentration, and the free sulfuric acid concentration. , the method of claim 1.
ガン溶液を得るとともに、ガス中のＳＯ＿２を実質的に
完全にスラリ中に吸収させることを特徴とする、請求項
１または２記載の方法。(3) Two or more of the bubble columns are used to obtain a highly concentrated manganese sulfate solution, and SO_2 in the gas is substantially completely absorbed into the slurry according to claim 1 or 2. the method of.
＿ｘ含有ガスと反応させ、得られた回収スラリを固液分
離することからなる、硫酸マンガン溶液の製造方法。(4) The raw material slurry containing manganese oxide ore is
A method for producing a manganese sulfate solution, which comprises reacting with a _x-containing gas and separating the obtained recovered slurry into solid and liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6894789A JPH02248327A (en) | 1989-03-20 | 1989-03-20 | Production of manganese sulfate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6894789A JPH02248327A (en) | 1989-03-20 | 1989-03-20 | Production of manganese sulfate solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02248327A true JPH02248327A (en) | 1990-10-04 |
Family
ID=13388368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6894789A Pending JPH02248327A (en) | 1989-03-20 | 1989-03-20 | Production of manganese sulfate solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02248327A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411997C (en) * | 2005-02-01 | 2008-08-20 | 桂林市孟泰矿产技术开发有限责任公司 | Method of recovering manganese sulfate from low-grade manganese carbonate and manganese oxide |
| CN101898798A (en) * | 2010-03-19 | 2010-12-01 | 深圳市东江环保股份有限公司 | Method for preparing manganese sulfate |
| WO2010096887A3 (en) * | 2009-02-26 | 2011-11-17 | Mineração Tabiporã Ltda | Process of production of manganese sulfate from the pirolusite chemical reaction |
| JP2013245159A (en) * | 2012-05-28 | 2013-12-09 | Guizhou Redstar Developing Co Ltd | Method for comprehensively treating claus tail gas and producing manganese sulfate |
| JP2014005191A (en) * | 2012-06-26 | 2014-01-16 | Guizhou Redstar Developing Co Ltd | Methods for preparing and controlling particle size of low-bet trimanganese tetroxide, and trimanganese tetroxide |
| CN104556233A (en) * | 2014-12-23 | 2015-04-29 | 中国地质科学院郑州矿产综合利用研究所 | Utilization method of manganese oxide ore |
| CN109354071A (en) * | 2018-11-21 | 2019-02-19 | 安徽工业大学 | A method of LITHIUM BATTERY manganese sulfate is produced using manganese tailing and Titanium white waste sulfuric acid |
| CN110357164A (en) * | 2019-07-08 | 2019-10-22 | 四川大学 | The method that manganese oxide ore pulp recycles high-efficiency flue gas desulfurization coupling manganese sulfate green purifying |
-
1989
- 1989-03-20 JP JP6894789A patent/JPH02248327A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411997C (en) * | 2005-02-01 | 2008-08-20 | 桂林市孟泰矿产技术开发有限责任公司 | Method of recovering manganese sulfate from low-grade manganese carbonate and manganese oxide |
| WO2010096887A3 (en) * | 2009-02-26 | 2011-11-17 | Mineração Tabiporã Ltda | Process of production of manganese sulfate from the pirolusite chemical reaction |
| CN101898798A (en) * | 2010-03-19 | 2010-12-01 | 深圳市东江环保股份有限公司 | Method for preparing manganese sulfate |
| JP2013245159A (en) * | 2012-05-28 | 2013-12-09 | Guizhou Redstar Developing Co Ltd | Method for comprehensively treating claus tail gas and producing manganese sulfate |
| JP2014005191A (en) * | 2012-06-26 | 2014-01-16 | Guizhou Redstar Developing Co Ltd | Methods for preparing and controlling particle size of low-bet trimanganese tetroxide, and trimanganese tetroxide |
| CN104556233A (en) * | 2014-12-23 | 2015-04-29 | 中国地质科学院郑州矿产综合利用研究所 | Utilization method of manganese oxide ore |
| CN109354071A (en) * | 2018-11-21 | 2019-02-19 | 安徽工业大学 | A method of LITHIUM BATTERY manganese sulfate is produced using manganese tailing and Titanium white waste sulfuric acid |
| CN109354071B (en) * | 2018-11-21 | 2020-11-24 | 安徽工业大学 | Method for producing battery-grade manganese sulfate by using manganese tailings and waste sulfuric acid of titanium white |
| CN110357164A (en) * | 2019-07-08 | 2019-10-22 | 四川大学 | The method that manganese oxide ore pulp recycles high-efficiency flue gas desulfurization coupling manganese sulfate green purifying |
| CN110357164B (en) * | 2019-07-08 | 2022-03-15 | 四川大学 | Method for green purification of manganese oxide ore slurry by coupling circulating efficient flue gas desulfurization with manganese sulfate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2487137B1 (en) | Method for preparing manganese sulfate monohydrate by desulfurizing fume with middle-low grade manganese dioxide ore | |
| US4011298A (en) | Method for simultaneous removal of SOx and NOx | |
| IE44311B1 (en) | Method of extracting and recovering mercury from gases | |
| AU2013299456A1 (en) | Process for converting FGD gypsum to ammonium sulfate and calcium carbonate | |
| US3226192A (en) | Process of treating waste gas containing sulfur oxide | |
| Maree et al. | Treatment of mine water for sulphate and metal removal using barium sulphide | |
| JPH02248327A (en) | Production of manganese sulfate solution | |
| US5362460A (en) | Magnesium separation from dolomitic phosphate by sulfuric acid leaching | |
| US3868444A (en) | Process for the preparation of porous sodium bicarbonate | |
| CN102745725B (en) | The method that magnesium sulfate monohydrate is produced using desulfurization waste liquor | |
| US3983225A (en) | Recovery of sulfur from sulfur dioxide rich aqueous absorbents | |
| EP1486460B1 (en) | Process and apparatus for preparing calcium thiosulfate solution | |
| CN106185836A (en) | High-pure anhydrous sodium sulfide production method | |
| US3965242A (en) | Method for desulfurizing exhaust gas by alkali sulphite-gypsum process | |
| CN101663241A (en) | Porous iron oxide, process for producing the same, and method of treating water | |
| US6214313B1 (en) | High-purity magnesium hydroxide and process for its production | |
| US3251649A (en) | Process of producing sulfuric acid | |
| US2951741A (en) | Process for treating complex ores | |
| CN102688665B (en) | Method for comprehensively treating Klaus tail gas and producing manganese sulfate | |
| JPS62225226A (en) | Wet stack-gas desulfurization facility | |
| US4038368A (en) | Process for removing oxides of nitrogen and sulfur from exhaust gases | |
| US4411875A (en) | Dual alkali process for combustion gas cleaning | |
| US4610853A (en) | Process for producing purified monoammonium phosphate from wet process phosphoric acid | |
| JPS62270421A (en) | Manufacture of potassium manganate for industrial manufacture of potassium permanganate from natural ore or manganese dioxide compounds | |
| CN110357164A (en) | The method that manganese oxide ore pulp recycles high-efficiency flue gas desulfurization coupling manganese sulfate green purifying |