CN103620069A - Manganese recovery method - Google Patents

Abstract

Provided is a method of economically recovering manganese from low-grade minerals and manganese-containing waste. Iron-reducing bacteria and a manganese-containing substance to be treated are mixed in a treatment solution containing trivalent iron ions, the trivalent iron ions are reduced to divalent iron ions by means of the iron-reducing bacteria, manganese ions are leached from the treated substance into the aforementioned treatment solution with the divalent iron ions as reducing agent, the obtained leachate is solid-liquid separated, the manganese ions contained in the separated liquid are insolubilized (solidified) mainly as oxides, and the obtained manganese oxides are precipitated, separated, and recovered.

Description

Manganese recovery method

Technical field

The present invention relates to the iron work by product from containing manganese composition, low-grade mineral, used battery etc. to reclaim the technology as the manganese of valuable metal.

Background technology

From low-grade raw ore or refining steel or iron work by product, reclaim specific valuable metal at present because the reason of cost also has difficulties.But, in recent years, due to the exhaustion of metals resources and the rising of transaction value etc., need to from such material, reclaim valuable metal.For example, as the manganese of one of valuable metal, in a plurality of fields of industrial community, all become necessary metal, in the future, probably its demand will be over reserve.

Particularly, in iron work, because a large amount of manganese that consumes is as steelmaking feed, therefore, in ironmaking field, guarantee that the problem in manganese source is very severe.In the iron work by products such as the dust that produce in a large number on the other hand,, sludge, slag, contain more manganese in iron work.Therefore, expect significantly to eliminate the problems referred to above by establishing the technology that reclaims manganese and recycle it as steelmaking feed from iron work by product.

At this, as the method that reclaims valuable metal from mineral, known following method: mineral are contacted with the treatment solution of acid or alkali, and contained valuable metal it is leached in treatment solution in dissolution of minerals, neutralizes by selection the valuable metal leaching in this treatment solution and reclaim.In addition, reclaim valuable metal from low-grade mineral in the situation that, from the angle of cost, general leaching valuable metal the method that reclaims from object mineral such as the acid of using sulfuric acid of adopting.

But, for use the acid such as sulfuric acid as treatment solution for reclaiming the method for valuable metal object mineral, its cost is still very high, under different situations, the unbalanced situation of the cost of the valuable metal of input cost and recovery is more, is suitable for example limited.In addition, in using sour recovery, exist the more difficult leaching of manganese, the rate of recovery of a part of form to reduce such problem.

On the other hand, known following method also: by use microorganism make valuable metal ions from leaching of ores to treatment solution in, thereby reclaim valuable metal.According to the method, can make valuable metal from leaching of ores to treatment solution in and without using a large amount of sulfuric acid etc., therefore, can from mineral, reclaim valuable metal and can not cause the problems referred to above.

In addition, as mentioned above, the method for using microorganism to leach metal from mineral is called as Bioleaching method (Bioleaching), it is characterized in that, energy expenditure still less, lower to the threat of environment.So, think that Bioleaching can realize raising and the cost degradation of metal leaching rate, therefore, its effective ways as leaching valuable metal from low-grade mineral and receiving publicity.

For example, following technology has been proposed in patent documentation 1: make the effect of iron reducing bacteria, 3 valency iron are reduced into divalent iron, the metal (cobalt, nickel, manganese etc.) comprising in the group of using described divalent iron to make to be comprised of metal oxide and metal hydroxides leaches, generate leach liquor and residue, described leach liquor is separated with residue, reclaim the metal of expectation.Particularly, it is to put into by leaching processing substratum, iron reducing bacteria and metal oxide or metal hydroxides the technology that reactor leaches processing, more specifically, following technology has been proposed: use step stirring-type reactor, on one side stir culture base makes metal oxide etc. that sedimentation not occur, regulate the maximum pH leaching in processing to be below 8.5, to be preferably neutrality (for example pH7.5 is following) on one side, integral body is made as to preferred specific pH scope and carries out the leaching of metal.According to this technology, can reclaim contained valuable metal (cobalt, nickel) in leach liquor by known method, and use it for the purposes of expectation.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-113116 communique

Summary of the invention

The problem that invention will solve

But, in patent documentation 1, about reclaiming the method for valuable metal contained in leach liquor, there is no concrete record.Therefore, according to the difference of recovery method, the iron-containing liquor of high density is discarded after a single use, and worries that it is uneconomical.

; in the situation that contained manganese leaches in making object being treated (metal oxide etc.) according to the technology of patent documentation 1 proposition, need to from the leach liquor that contains mn ion and iron ion (leaching while processing by divalent iron being oxidized to the 3 valency iron that obtain or also having not oxidized and remaining divalent iron), reclaim manganese.

As the known method of the metal of separated expectation the leach liquor from containing many kinds of metal ions, in oriented leach liquor, add medicament etc. and carry out the optionally method of precipitate and separate metal kind.If apply the method, the leach liquor that comprises mn ion and iron ion is processed, in most cases, first, owing to easily producing the precipitated separation of iron ion of insoluble salt, therefore, need to make mn ion remain in separated with iron in leach liquor after, separated manganese from leach liquor.In such method, the recovery of manganese needs the separation circuit of twice, the problem that exists operation to complicate.In addition, if from leach liquor precipitate and separate iron ion, be difficult to iron-containing liquor (leach liquor) to recycle.

On the other hand, when reclaiming valuable metal from leach liquor, also consider to use electrolytic process, make spent ion exchange resin, resin etc. as the absorption method of sorbing material.But, for common electrolytic process, need to make iron dissolve in organic solvent at the material of the formation complex compounds such as leading portion interpolation and iron, generally by being called the water/organic solvent of separatory, iron is extracted out and is separated to organic solvent layer from water layer, the manganese of target need to be residued in to the separation circuit in tank, and need to use a large amount of organic solvents.In addition, treatment process also increases, but also will consume huge electric weight.In addition, the sorbing material using in absorption method is conventionally comparatively expensive, but also needs disengaging, the recovery process after fractionation by adsorption.Therefore,, in the situation that want to reclaim manganese from the such a large amount of object being treateds of iron work by product, if use electrolytic process and absorption method, recovery cost is huge.

In addition, in the manganese using as steelmaking feed, in order to prevent sneaking into impurity, particularly carbon (C) and phosphorus (P) to cast steel (Milling Steel), require highly purified manganese in iron work.Therefore, different according to the concentration of the C of reclaimed manganese and the such impurity of P, can not use as steelmaking feed.

As mentioned above, according to the purposes of the manganese reclaiming, it is also important fully reducing its foreign matter content, but in the prior art, not to reducing the research of impurity contained in the manganese reclaiming.

The present invention carries out in view of the above problems, its object is to provide a kind of manganese recovery method, manganese contained in the object being treated that contains manganese is leached in leach liquor, then by the manganese concentration and recovery leaching, and reusable leach liquor, thus, can be at an easy rate from low-grade mineral and containing reclaiming manganese manganese waste, by product.

The method of dealing with problems

The inventor conducts in-depth research the method for settlement separate target manganese, in the treatment solution that contains 3 valency iron, mix object being treated and the iron reducing bacteria that contains manganese, make the effect of iron reducing bacteria that 3 valency iron are reduced into divalent iron, the effect that utilizes this divalent iron to be oxidized to 3 valency iron leaches in treatment solution mn ion from the object being treated that contains manganese, the leach liquor that has leached mn ion is carried out to solid-liquid separation, in parting liquid from solid-liquid separation, reclaim manganese, now, the state that solvability iron is residued in parting liquid is undertaken settlement separate by target manganese.Its result, finds by parting liquid being implemented to given oxide treatment, makes mn ion contained in parting liquid mainly insoluble with the form of Mn oxide, thereby can carry out precipitate and separate.

Fig. 1 is manganese and the redox potential (ORP) of iron and the state graph of pH (Eh-pH figure) in the aqueous solution of 25 ℃.As shown in Figure 1, in Eh-pH figure, the region of the region of manganese precipitation and iron precipitation is almost consistent except the region with zero encirclement in Fig. 1, and the region of iron precipitation is wider.Therefore,, if (the having carried out ionization) region of all dissolving from manganese, iron changes the state of redox potential (ORP), pH, in nearly all region, iron is preferentially with the form solidification of oxide compound or oxyhydroxide and precipitate.But think, having existence in region at low pH, high ORP (in Fig. 1 with zero region surrounding) only is mainly that manganese forms oxide compound and the region of solidification precipitation.

Therefore, the inventor etc. expect, by being adjusted into, the pH of the above-mentioned parting liquid that contains mn ion and 3 valency iron ions and redox potential (ORP) in Eh-pH figure, mainly with manganese, form oxide compound and pH and the redox potential (ORP) of the region of solidification precipitation the region of zero encirclement (in the Fig. 1 with), can keep being dissolved with in liquid the state as the iron ion of the matrix of iron reducing bacteria, mainly make manganese form oxide compound and make its insoluble and precipitation.

The inventor etc. are found that of research further, by reducing the pH of above-mentioned parting liquid with acid and making ozone play a role to improve the ORP of above-mentioned parting liquid, can be cheap and from the above-mentioned parting liquid that contains mn ion and 3 valency iron ions, preferentially mainly make easily manganese form oxide compound and solidification.

In addition, in described parting liquid, contain 3 abundant valency iron ions or further also contain divalent iron ion.Therefore, that precipitation of iron ions contained in above-mentioned parting liquid is separated by iron ion is remained in parting liquid, can be using above-mentioned parting liquid as for the treatment solution that mn ion leaches from object being treated is recycled.

Find in addition, by using specific iron reducing bacteria that 3 valency iron in treatment solution are reduced into divalent iron, can leach at a high speed, efficiently low-grade manganese contained in object being treated.

In addition, inventor etc. is studied reducing the method for impurity (carbon, the phosphorus etc.) content of the manganese of final recovery.

In the situation that used the Bioleaching method (Bioleaching) containing germy treatment solution, treatment solution is conventionally containing the Multiple components that is useful on the Leaching reaction of the metal that promotes to utilize iron reducing bacteria.In the situation that the treatment solution that contains iron reducing bacteria contains the compositions such as 3 valency iron ions, electron donor, pH adjusting agent, pH buffer reagent.In addition, certainly also containing being useful on the necessary element making as the iron reducing bacteria growth of microorganism, i.e. carbon, phosphorus.If these compositions are not enough, iron reducing bacteria cannot be grown, and its result leaches metal and becomes difficult.Therefore, conventionally according to reclaiming the application target of metal, in treatment solution, contain the composition (C, P etc.) that can be used as impurity.

The inventor etc. find out that there are the following problems: the composition that can be used as impurity in treatment solution exists ratio to be also blended in regenerant according to it.And, further found that of research, by limiting the impurity concentration in treatment solution, can promote the leaching of mn ion from object being treated, can also reduce and from treatment solution, be transferred to the impurity level reclaiming in manganese, and then can reduce the impurity concentration that reclaims manganese simultaneously.

To obtaining the experiment of described understanding, be described.

First, prepared ironic citrate (III) medium standard solution as the treatment solution that contains 3 valency iron.General composition at this ironic citrate (III) medium standard solution is to contain carbon in ironic citrate (III), Trisodium Citrate, sodium formiate, in addition, contains phosphoric in SODIUM PHOSPHATE, MONOBASIC, in addition, contains carbon and phosphoric in peptone.These elements are the essential component of utilizing in the metal Leaching reaction that iron reducing bacteria carries out, and the concentration of various compositions (or content) is as follows.

Ironic citrate (III) trihydrate: 16.7g/L (56mM)

Trisodium citrate dihydrate (coordination agent): 10.3g/L (35mM)

SODIUM PHOSPHATE, MONOBASIC: 0.6g/L

Peptone: 0.5g

KCl：0.1g

NH ₄Cl：1.5g

The mineral solution of Wolfe: 10cm ³

The vitamin solution of Wolfe: 10cm ³

Sodium formiate (electron donor): 2.0g/L (30mM)

The value of the concentration of above-mentioned various compositions (or content) is the value in every 1L ironic citrate (III) medium standard solution.In addition, mM represents mmol/L.

At this, the inventor etc. infer, and carbon concentration and phosphorus concentration in ironic citrate (III) medium standard solution (treatment solution that contains 3 valency iron) can bring impact to the carbon concentration in the manganese of final recovery and phosphorus concentration.Using the treatment solution of concentration (or content) with above-mentioned various compositions as standard treatment solution, preparation with respect to this standard treatment solution by three kinds of ironic citrates (III) medium standard solution of following (A)～(C) change carbon concentration or phosphorus concentration as treatment solution, investigated the impact that carbon concentration in this substratum and phosphorus concentration bring manganese leaching yield.

(A) using the concentration of the SODIUM PHOSPHATE, MONOBASIC as phosphorus composition by the 0.6g/L ladder of standard treatment solution be down to 0g/L and the treatment solution (totally 4 kinds of concentration: 0.6g/L, 0.3g/L, 0.1g/L, 0g/L) that obtains.It should be noted that, the concentration (or content) of the composition beyond SODIUM PHOSPHATE, MONOBASIC is identical with standard treatment solution.In addition, the phosphorus concentration of the treatment solution in the situation that is 0g/L by the concentration of SODIUM PHOSPHATE, MONOBASIC is measured, result is 5mg/L (0.16mM).Think that it is from the composition beyond SODIUM PHOSPHATE, MONOBASIC.

(B) using the concentration of the ironic citrate as carbon component (III) trihydrate by 16.7g/L (56mM) ladder of standard treatment solution be down to 1.5g/L and the treatment solution that obtains.(totally 4 kinds of concentration: 16.7g/L, 7.5g/L, 3.0g/L, 1.5g/L).It should be noted that, for the concentration (or content) of the composition beyond ironic citrate (III) trihydrate, SODIUM PHOSPHATE, MONOBASIC is made as without adding, and other one-tenth is divided into identical with standard treatment solution.

(C) using the concentration of the Trisodium citrate dihydrate as carbon component by 10.3g/L (35mM) ladder of standard treatment solution be down to 0g/L and the treatment solution that obtains.(totally 4 kinds of concentration: 10.3g/L, 2.9g/L, 1.03g/L, 0g/L).It should be noted that, the concentration (or content) for the composition beyond Trisodium citrate dihydrate, is made as 1.5g/l by ironic citrate (III) trihydrate, and SODIUM PHOSPHATE, MONOBASIC is made as without adding, and other one-tenth is divided into identical with standard treatment solution.

In described (A)～(C), because the addition of the peptone that comprises carbon component or phosphorus composition and the sodium formiate that comprises carbon component is few, therefore, its concentration (or content) is separately made as identical with standard treatment solution.

To various ironic citrates (III) the medium standard solution (treatment solution that contains 3 valency iron) that adds above-mentioned (A)～(C) in step stirred vessel: 150cm ³, iron work the metallic dust producing in refining procedure (Mn:69 quality %, Fe:3 quality %) 0.75g and iron reducing bacteria shewanella? algae(NBRC103173 strain): 1 * 10 ⁷individual/cm ³, the temperature of mixed solution is remained on to about 30 ℃, implement bubbling and the stirring of the nitrogen of 24 hours to 144 hours, carried out leaching and processed.Then, by solid-liquid separation, gather leach liquor, measure the Mn concentration in leach liquor and calculate Mn leaching yield.By the results are shown in table 1～3 of they.

[table 1]

[table 2]

[table 3]

Table 1 is to use the treatment solution of above-mentioned (A) to carry out leaching for 24 hours the result of processing.As shown in table 1, at the SODIUM PHOSPHATE, MONOBASIC (NaH adding as standard treatment solution as phosphorus composition ₂pO ₄) situation and the situation of not adding between, the manganese leaching yield that leaches the treatment time and be 24 hours is not found larger difference.

Table 2 is to use the treatment solution of above-mentioned (B) to carry out leaching the result of processing.As shown in table 2, if reduce the concentration of the ironic citrate (III) that contains carbon component, the manganese leaching yield at initial stage reduces.But, when the leaching treatment time is 144 hours, even the concentration of the ironic citrate that contains carbon component (III) trihydrate is reduced in the situation of 1.5g/L, also obtained the manganese leaching yield equal with standard treatment solution situation.

Table 3 is to use the treatment solution of above-mentioned (C) to carry out leaching the result of processing.If reduce the concentration of the Trisodium Citrate that contains carbon component, manganese leaching yield significantly reduces, even if extend, leaches the treatment time, and leaching yield is also still very low.That is, can say, from manganese leaching yield viewpoint, consider, preferably not reduce the Trisodium citrate dihydrate concentration in treatment solution and make it keep the concentration (10.3g/L) equal with standard treatment solution situation.

By the ironic citrate in treatment solution (III) trihydrate concentration be made as 1.5g/l (5mM), the carbon concentration that Trisodium citrate dihydrate concentration is made as in the treatment solution in the situation of 10.3g/L (35mM) is 270mM.

In addition, the inventor etc. carry out and above-mentioned same experiment repeatedly, and the impurity concentration of the manganese of final recovery (carbon concentration and phosphorus concentration) is measured.It found that, if by the carbon concentration in treatment solution be limited in 300mM following, phosphorus concentration is limited in below 0.5mM, the impurity concentration of the final manganese reclaiming significantly reduces, and can obtain the recovery manganese that can be applicable to steelmaking feed etc.

The present invention completes based on above-mentioned discovery, and its purport is as follows.

[1] a manganese recovery method, the method has following operation:

Leach operation, in the treatment solution that contains 3 valency iron ions, mix object being treated and the iron reducing bacteria that contains manganese, by described iron reducing bacteria, described 3 valency iron ions are reduced into divalent iron ion, take this divalent iron ion to leach into described treatment solution from described object being treated as reductive agent makes mn ion;

Solid-liquid separation process, the leach liquor that this leaching operation is obtained carries out solid-liquid separation;

Insoluble operation, makes it insoluble mn ion oxidation contained in parting liquid after this solid-liquid separation process; And

Recovery process, the manganese composition precipitate and separate that this insoluble operation is obtained and reclaiming.

[2] above-mentioned [1] described manganese recovery method, wherein, using reclaimed the recovery that contains ferric ion of manganese composition from described parting liquid, parting liquid is as the treatment solution recycling of described leaching operation.

[3] the described manganese recovery method in above-mentioned [1] or [2], wherein, described insoluble operation is the parting liquid effect making under acidic conditions after ozone and described solid-liquid separation process, thus mn ion oxidation is made to its insoluble operation.

[4] the manganese recovery method described in any one in above-mentioned [1]～[3], wherein, described object being treated is iron work by product and/or low grade ore and/or used battery and/or contains manganese powder dirt and/or contain manganese ore mud and/or contain manganese mud.

[5] the manganese recovery method described in any one in above-mentioned [1]～[4], wherein, in described insoluble operation, take out termly or continuously the liquid in insoluble processing, the colour-change of the solution part of the liquid that observation post takes out, differentiates the oxidizing reaction terminal of mn ion thus.

[6] the manganese recovery method described in any one in above-mentioned [1]～[5], wherein, the treatment solution in described leaching operation is the treatment solution that has limited carbon concentration and phosphorus concentration.

[7] above-mentioned [6] described manganese recovery method, wherein, described carbon concentration is below 300mM, described phosphorus concentration is below 0.5mM.

The effect of invention

According to manganese recovery method of the present invention, manganese class contained in manganese mineral etc. can be concentrated and reclaims with the enrichment factor compared with high under such more stable condition under room temperature, normal atmosphere, simultaneously, by Reusability treatment solution, can reduce the expense that manganese reclaims, industrial, play significant effect.In addition, manganese recovery method of the present invention, due to can be cheap and reclaim manganese easily from a large amount of object being treateds, therefore, particularly, be very effective as the method that reclaims manganese in a large amount of iron work by products that produce from iron work.

Accompanying drawing explanation

Fig. 1 is manganese and the redox potential (ORP) of iron and the state graph of pH (Eh-pH figure) in the aqueous solution.

Fig. 2 (a) is the schema of a mode of explanation manganese recovery method of the present invention; Fig. 2 (b) is the schema of explanation manganese recovery method another way of the present invention.

Fig. 3 illustrates the figure that the discarded drying battery of test is pulverized the manganese leaching yield of the embodiment considering to be worth doing.

Fig. 4 is the figure of the composition in the solid being illustrated under acidic conditions when the manganese leach liquor of embodiment is carried out to ozone diffusion.

Fig. 5 is the figure that is illustrated under acidic conditions the manganese recovery ratio when manganese leach liquor of embodiment is carried out to ozone diffusion.

Fig. 6 is illustrated under acidic conditions the figure that manganese leach liquor of the present invention is carried out to the variation of manganese recovery ratio in the situation of ozone DIFFUSION TREATMENT and filtrate color.

Nomenclature

1 ... object being treated

2 ... broken process

3 ... leach operation

4 ... treatment solution

5 ... leach mud (leach liquor)

6 ... solid-liquid separation process

7 ... residue

8 ... unreacted residue

9 ... foldback residue

10 ... leach liquor (parting liquid) containing manganese composition

10a ... parting liquid after reclaiming

11 ... insoluble operation

12 ... acid

13 ... ozone generating apparatus

14 ... recovery process

15 ... Mn oxide

16 ... in and operation

17 ... discharge water (ブ ロ ー water)

18 ... alkali

19 ... separated, observation groove

Embodiment

Below, the present invention is at length described.

Manganese recovery method of the present invention is characterised in that, the method has following operation: leach operation, in the treatment solution that contains 3 valency iron ions, mix object being treated and the iron reducing bacteria that contains manganese, by described iron reducing bacteria, described 3 valency iron ions are reduced into divalent iron ion, take this divalent iron ion to leach into described treatment solution from described object being treated as reductive agent makes mn ion; Solid-liquid separation process, the leach liquor that this leaching operation is obtained carries out solid-liquid separation; Insoluble operation, makes it insoluble mn ion oxidation contained in parting liquid after this solid-liquid separation process; And recovery process, the manganese composition precipitate and separate that this insoluble operation is obtained and reclaiming.In addition, also can in above-mentioned leaching operation, recycle parting liquid after the recovery that comprises the 3 valency iron ions that reclaimed manganese composition from above-mentioned parting liquid.

Fig. 2 (a) is the schema that an embodiment of the invention are shown.As shown in Fig. 2 (a), in the present invention, first, as required the object being treated that contains manganese 1 is pulverized by broken process 2.Then, in leaching operation 3, object being treated 1, the treatment solution 4 that contains 3 valency iron ions and iron reducing bacteria are mixed, obtain leaching mud (leach liquor) 5.At this, leach in operation 3, by iron reducing bacteria, 3 valency iron ions are reduced into divalent iron ion, meanwhile, by making this divalent iron ion to the manganese composition effect in object being treated 1, the manganese composition in object being treated 1 is dissolved.

As object being treated 1, be the material that contains manganese, such as using containing manganese powder dirt and/or containing iron work by product, low grade ore, used batteries etc. such as manganese ore mud.In addition, as the shape of object being treated 1, except the solid that contains manganese, can also enumerate containing manganese powder dirt and/or contain manganese ore mud and/or contain manganese mud etc.

In the situation that using used battery as object being treated 1, preferably by precrushing, screening etc., the metal separation such as the iron that housing is used, make the mixture of positive electrode material, negative material.

In addition,, as the manganese composition comprising in object being treated 1, can enumerate MnO ₂, Mn ₂o ₃, Mn ₃o ₄deng.

Object being treated 1 quilt is for mixing with treatment solution 4 and making mn ion leach into the leaching operation 3 in treatment solution 4.But if larger to the particle diameter of object being treated 1 that leaches the stage that operation 3 shifts, specific surface area reduces, solid-liquid contact area (contact area of object being treated 1 and treatment solution 4) reduces, and leaching velocity reduces.In addition, in the situation that using intermittent reaction container to leach operation 3, if the particle diameter of also worrying object being treated 1 is more greatly, leach while processing object being treated 1 can sedimentation, thereby can not leach fully processing.

Due to above reason, in the present invention, in the situation that object being treated 1 is solid, take and reduce particle diameter to improve the reaction efficiency leaching in operation 3 be object, broken process 2 is preferably set.Particle diameter is less, and reaction efficiency more improves, and more can shorten the reaction times in leaching operation 3.Therefore, in the present invention, preferably making to the particle diameter that leaches the object being treated 1 in the stage that operation 3 shifts is below 100mm, more preferably below 100 μ m.But, from the viewpoint of the complexity of solid-liquid separation, consider, more than preferably the particle diameter of object being treated 1 being made as to 1 μ m.

As breaking method, can use jaw crusher, rotate the known breaking methods such as grinding machine.In addition,, in the situation that the particle diameter of object being treated 1 is enough little, also can omit broken process 2.

Object being treated 1 by above-mentioned acquisition is transferred to leaching operation 3.In leaching operation 3, treatment solution 4 and object being treated 1 are mixed, the effect that utilization is oxidized to 3 valency iron ions by divalent iron ion makes mn ion be leached to treatment solution 4 from object being treated 1.That is, in leaching operation 3, by the reaction of following (i), divalent iron is oxidized to 3 valency iron, and meanwhile, object being treated 1 is reduced, and mn ion leaches in treatment solution 4.

Fe ²⁺+ Mn oxide compound or oxyhydroxide (MnO for example ₂, Mn ₂o ₃, Mn ₃o ₄) → Fe ³⁺+ Mn ²⁺(solubility) ... (i)

At this, as treatment solution 4, also can use the treatment solution that has added divalent iron ion.But, in the present invention, preferably, the treatment solution that use comprises 3 valency iron ions, in this treatment solution, mix object being treated and iron reducing bacteria, above-mentioned 3 valency iron ions are reduced into divalent iron ion, meanwhile, using this divalent iron ion as reductive agent, mn ion are leached into treatment solution 4 from object being treated 1.

Iron reducing bacteria be from electron donor (organism etc.) give and accept electronics, and by being supplied with the bacterium growing as the iron breathing of 3 valency iron ions of electron acceptor, its reaction having by following (ii) is reduced into 3 valency iron the effect of divalent iron.

Fe ^3＋＋e ^-→Fe ^2＋…(ii)

Therefore,, if mix object being treated 1 and iron reducing bacteria in the treatment solution that comprises 3 valency iron ions, iron reducing bacteria is used the electronics (e from electron donor ^-) by 3 valency iron ion (Fe ³⁺) direct-reduction and generate divalent iron ion (Fe ²⁺), result can obtain the treatment solution that comprises divalent iron and iron reducing bacteria.The divalent iron generating due to reaction by above-mentioned (ii) contributes to the reaction of above-mentioned (i), therefore, in leaching operation 3, can make mn ion leach in treatment solution 4.

As the 3 valency iron and the iron reducing bacteria that use in the present invention, can enumerate the bacterium of kind shown below.In addition, to the iron that adds iron reducing bacteria in the treatment solution that comprises 3 valency iron ions simultaneously, breathe required electron acceptor (above-mentioned 3 valency iron ions) and electron donor.In addition, preferably, by adding any one the above and pH buffer reagent in the acid shown in following, alkali, pH adjusting agent, the pH for the treatment of solution is adjusted into given pH described later.In addition, certainly need to exist simultaneously and make necessary element of the growth of iron reducing bacteria etc.

< iron reducing bacteria >

As the iron reducing bacteria using in leaching operation 3 of the present invention, for example, can enumerate geobacter? metallireducenslovley et al. (ATCC53774, DSM7210), desulfomonas palmitatiscoates et al. (ATCC51701, DSM12931), desulfuromusakysingiiliesack & Finster (DSM7343), pelobacter? venetianusschink & Stieb (DSM2395), shewanella? algaeshimidu et al.1990 (NBRC103173, IAM14159, ATCC51181), ferrimonas? balearicarossello-Mora et al. (DSM9799), aeromonas? hydrophilasubsp. hydrophila(Chester) Stanier (DSM30014), sulfurospirillum? barnesiistolz et al. (ATCC700032, DSM10660), wolinella? succinogenes(Wolin et al.) Tanner et al. (DSM1740, ATCC29543), desulfovibrio? desulfuricanssubsp. desulfuricans(Beijerinck) Kluyver & van Niel (DSM642, ATCC29577), geothrix? fermentanscoates et al. (ATCC700665), deferribacter? thermophilusgreene et al. (DSM 14813), thermotoga? maritimestetter & Huber (DSM3109) etc.

In addition, also can use in the present invention iron reduction archeobacteria, as iron reduction archeobacteria, for example, can enumerate archaeoglobus? fulgidusstetter (ATCC49558, DSM4304), pyrococcus? furiosusfiala & Setter (ATCC49587, DSM3638), pyrodictiumabyssi? pleyand Stetter (ATCC49828, DSM6158), methanothermococcus? thermolithotrophicus(Huber et al.) Whitman (DSM2095, JCM10549, ATCC35097) etc.

At this, for above-mentioned iron reducing bacteria, iron reduction archeobacteria, although recorded bacterial strain symbol in each parantheses, be not limited thereto.

In addition, the synonym of above-mentioned bacterial classification etc. are of equal value with above-mentioned bacterial classification, and the bacterial classification under above-mentioned bacterial strains is also of equal value with above-mentioned bacterial classification.

It should be noted that, in this manual, the situation of with good grounds generic name (comprising abbreviation) and kind pet name specified strain.

In above-mentioned, the title that bacterial strain is preserved office, facility is expressed as follows respectively the meaning.

ATCC：American?Type?Culture?Collection，Manassas，VA，USA

DSM：Deutsche?Sammlung?von?Mikroorganismen?und?Zellkulturen?GmbH(DSMZ)，Braunschweig，Germany

NBRC：NITE?Biological?Resource?Center，Chiba，Japan

[the (System Pin Evaluation Price Ji Intraoperative Ji Disk Machine Agencies Sheng Wu Left Transfer Capital Yuan Bu Door of (solely) goods assessment technology fundamental mechanism Biological Genetic Resources department) (NITE Biological information resources center)]

JCM, IAM:Japan Collection of Microorganisms, RIKEN, Saitama, Japan[(is only) RIKEN's Biological resources center microbial material exploitation chamber (RIKEN's バ イ オ リ ソ ー ス セ ン タ ー microorganism Cai Liao development chamber) (JCM)]

As iron reducing bacteria, from the viewpoint of open air processing complexity, consider, preferably facultative anaerobic bacteria.For example, in above-mentioned bacterial classification, can enumerate the bacterium of recording as iron reducing bacteria.

In addition, as iron reducing bacteria, from the viewpoint of open air processing complexity, consider, preferably on the bacterium of normal temperature region growing.For example, in above-mentioned bacterial classification, can enumerate the bacterium (except Geothrix fermentans and Thermotoga maritime) of recording as iron reducing bacteria.

In addition, as iron reducing bacteria, preferred Geobacter metallireducens or Shewanella algae, more preferably Shewanella algae.

The quantity of iron reducing bacteria is not particularly limited.But, from the viewpoint of further raising leaching velocity, leaching efficiency, consider, when leaching operation, as initial value, in preferably treatment liquid, contain 1.0 * 10 ¹³individual/m ³above, more preferably contain 1.0 * 10 ¹³～1.0 * 10 ¹⁵individual/m ³, further preferably contain 5.0 * 10 ¹³～2.0 * 10 ¹⁴individual/m ³.

< 3 valency iron ion >

The 3 valency iron ions that use in leaching operation 3 of the present invention are not particularly limited.But preferably above-mentioned 3 valency iron ions add in treatment solution with the form of water miscible 3 valency molysite.In addition, the preferred inorganic acid salt of above-mentioned water miscible 3 valency molysite or organic acid salt.

As above-mentioned inorganic acid salt, can enumerate such as iron(ic) chloride (III), iron nitrate (III), ferric sulfate (III), etc.On the other hand, as above-mentioned organic acid salt, can enumerate such as ironic citrate (III), ironic formiate (III), ironic acetate (III) etc.

The concentration of 3 valency iron ions is not particularly limited, but considers from the viewpoint of further raising leaching velocity, leaching efficiency, when leaching operation, as initial value, in preferably treatment liquid, contains 10mol/m ³above, more preferably contain 10～200mol/m ³, further preferably contain 25～100mol/m ³.

< electron donor >

Electron donor can suitably be selected according to above-mentioned iron reducing bacteria.For example, in the situation that iron reducing bacteria is Geobacter metallireducens or Shewanella algae, can use organism as electron donor.

As above-mentioned organism, such as organism [carboxylate salt (the fat formula carboxylate salt (soap): formate, acetate etc. that can enumerate carbonatoms 1～7, aromatic carboxylic acid salt: benzoate etc., keto-earboxylic acid (オ キ ソ カ Le ボ Application acid) salt: pyruvate salt etc., other carboxylate salt: lactic acid salt etc.), alcohol (ethanol etc.), unsaturated aromatic series (cresylol (toluene phenol) etc.)] etc.In addition, as above-mentioned organism, except comprising carbon, hydrogen, oxygen, can certainly comprise for example nitrogen, sulphur, other element.In addition, as above-mentioned organism, be not limited to the organism of water-soluble or water dispersible, also can comprise neither water-soluble organic particulate that neither water dispersible.

The concentration of electron donor is not particularly limited.But the initial value during as leaching operation, preferably contains 100mol/m ³above.

< acid, alkali, pH adjusting agent >

Can be selected from more than one in acid, alkali, pH adjusting agent pH by treatment solution 4 and be adjusted into given pH described later to adding in above-mentioned treatment solution 4.

Above-mentioned acid is not particularly limited, can example example hydrochloric acid, the organic acids such as mineral acid, formic acid, acetic acid, lactic acid, citric acid, succsinic acid, oxysuccinic acid such as sulfuric acid, nitric acid.Above-mentioned alkali is also not particularly limited, and can use such as sodium hydroxide, potassium hydroxide, their aqueous solution etc.In addition, above-mentioned pH adjusting agent is also not particularly limited, and can use such as salt of wormwood, sodium bicarbonate etc.

< pH buffer reagent >

In leaching operation 3, follow carrying out pH and may changing of reaction.Therefore, also can add above-mentioned pH adjusting agent and/or pH buffer reagent is suitably adjusted pH, suppress to change.

The pH buffer reagent adding to above-mentioned treatment solution 4 is so long as have the buffer reagent of surge capability in neutral pH scope, be not particularly limited, can enumerate for example acetic acid/sodium acetate, citric acid/sodium citrate, lactic acid/Sodium.alpha.-hydroxypropionate, phosphoric acid/sodium phosphate, tartrate/sodium tartrate, N-(2-kharophen)-2-aminoethyl sulfonic acid, N-(2-kharophen) iminodiethanoic acid, N, two (2-the hydroxyethyl)-2-aminoethyl sulfonic acid of N-, N, two (2-hydroxyethyl) glycine of N-, 2-[4-(2-hydroxyethyl)-1-piperazinyl] ethyl sulfonic acid, 2-[4-(2-hydroxyethyl)-1-piperazinyl] ethyl sulfonic acid sodium, MES, 2-hydroxyl-3-morpholine propanesulfonic acid, piperazine-1, 4-two (2-ethanesulfonic acid), piperazine-1, 4 – two (2-hydroxyl-3-N-morpholinopropanesulfonic acid) etc.

As the pH buffer reagent adding in above-mentioned treatment solution 4, can use the buffer reagent that can play a role as above-mentioned electron donor.At iron reducing bacteria, be for example shewanella? algaesituation under, lactic acid/Sodium.alpha.-hydroxypropionates etc. can be used as pH buffer reagent and play a role, and also can play a role as electron donor simultaneously.In addition, as the pH buffer reagent adding in above-mentioned treatment solution 4, can use and can form with the mn ion leaching from object being treated 1 buffer reagent of complex compound.For example, citric acid/sodium citrate etc. can with Mn ²⁺form complex compound.

It should be noted that, do not damaging object of the present invention and do not damaging in the scope of pH shock absorption, above-mentioned pH buffer reagent can be used separately a kind of or combine two or more uses with content arbitrarily.

＜pH＞

There is some difference according to bacterial classification or bacterial strain difference in the iron reducing bacteria using in the present invention, but its growth optimal pH is in neutral pH scope.But, in leaching operation 3, follow the pH that carries out treatment solution 4 of reaction likely to change.

Therefore, the pH of above-mentioned treatment solution 4 as long as be just not particularly limited near 7.0.But, in the situation that the pH for the treatment of solution 4 changes, by be controlled at more than 5.0 and 9.0 following, preferably control be more than 6.0 and 8.0 following, further preferably control is more than 6.5 and below 7.5, thus, can realize efficient leaching.

In addition, according to the purposes that reclaims manganese, require to reduce as far as possible the impurity in this manganese.For example, in the situation that using recovery manganese as steelmaking feed, for anti-blocking, phosphorus, to cast steel, sneak into, require highly purified recovery manganese.

In manganese recovery method of the present invention, aspect carbon concentration and phosphorus concentration in reducing the final manganese reclaiming, preferably above-mentioned treatment solution 4 is made to the treatment solution that has limited carbon concentration and phosphorus concentration.That is, preferably regulate its composition to make in the composition of the treatment solution before adding iron reducing bacteria carbon concentration and phosphorus concentration for certain is below value.

In order to obtain highly purified Mn oxide, preferably making the carbon concentration before the interpolation iron reducing bacteria of above-mentioned treatment solution 4 is that 300mM is following, phosphorus concentration is below 0.5mM.In addition, more preferably making carbon concentration is that 270mM is following, phosphorus concentration is below 0.16mM.

But, if extremely reduce above-mentioned carbon concentration and phosphorus concentration, can hinder the growth of iron reducing bacteria, manganese leaching yield is produced to detrimentally affect.Therefore, preferably making above-mentioned carbon concentration is that 100mM is above, phosphorus concentration is more than 0.05mM.

State in the use such treatment solution 4 and implement to leach in the situation of operation 3, under the state that has intercepted oxygen, make object being treated 1 contact and mix with treatment solution 4.Its reason is, if there is oxygen, to worry that above-mentioned iron reducing bacteria can not carry out the reduction reaction from 3 valency iron to divalent iron.In addition, the temperature for the treatment of solution 4 preferably remains on 10～35 ℃.It should be noted that, extraction time changes according to leaching condition, but is generally 24～72 hours.

As mentioned above, if object being treated 1, iron reducing bacteria and the treatment solution 4 that comprises 3 valency iron ions are mixed, 3 valency iron ions in treatment solution 4 are reduced into as divalent iron ion by iron reducing bacteria.This divalent iron ion works with reductive agent for object being treated 1, divalent iron is oxidized to 3 valency iron, simultaneously, manganese in object being treated 1 leaches in treatment solution 4, thereby obtains the leaching mud (leach liquor) 5 that comprises mn ion and 3 valency iron ions or further also comprise unreacted divalent iron ion.By leaching the leaching mud (leach liquor) 5 of operation 3 acquisitions, be sent to solid-liquid separation process 6.

In solid-liquid separation process 6, above-mentioned leaching mud (leach liquor) 5 is carried out to solid-liquid separation.

While above-mentioned leaching mud (leach liquor) 5 being carried out to solid-liquid separation by solid-liquid separation process 6, can obtain leach liquor (parting liquid) 10 and residue (solid) 7 containing manganese composition as supernatant liquor composition.

The solid-liquid separating method using in solid-liquid separation process 6 can be for being selected from any means in gravity settling separation, filtration, centrifugation, press filtration, membrane sepn etc.In addition, in the situation that it is higher to leach the solids concn of mud 5, preferably use press filtration.

Containing mainly comprising mn ion and iron ion (3 valency iron ions or in addition divalent iron ion) in the leach liquor (parting liquid) 10 of manganese composition.In addition, in residue (solid) 7, mainly comprise the solidity composition outside the demanganization of iron reducing bacteria, object being treated 1.

Then, the leach liquor (parting liquid) 10 containing manganese composition is transferred to insoluble operation 11.On the other hand, owing to containing more iron reducing bacteria in residue (solid) 7, therefore, its part is returned to leaching operation 3 as returning to residue 9, meanwhile, a part is reclaimed to (with reference to Fig. 2 (a)) as unreacted residue 8.

In insoluble operation 11, the leach liquor (parting liquid) 10 containing manganese composition obtaining by solid-liquid separation process 6 is implemented to given insoluble processing, pH containing the leach liquor (parting liquid) 10 of manganese composition and redox potential (ORP) are adjusted into manganese and form oxide compound and make its insoluble (solidification) precipitation but iron not have the region of precipitation, in Eh-pH figure (Fig. 1) by pH and the redox potential (ORP) in the region of zero encirclement.Thus, be dissolved in containing the manganese in the leach liquor 10 of manganese composition preferential insoluble and form solid.This insoluble operation 11 is preferably made as and under acidic conditions, makes ozone and the operation that contains leach liquor (parting liquid) 10 effects of manganese composition, for example, preferably, containing after adding acid 12 in the leach liquor (parting liquid) 10 of manganese composition, by ozone generating apparatus 13, spread ozone.; preferably by adding acid 12 pH that regulate containing the leach liquor (parting liquid) 10 of manganese composition; by ozone, spread to regulate the redox potential (ORP) containing the leach liquor (parting liquid) 10 of manganese composition simultaneously; thus; pH containing the leach liquor 10 of manganese composition and redox potential (ORP) are adjusted into manganese forms oxide compound and solidification precipitation but the non-setting region of iron, in Eh-pH figure (Fig. 1) by pH and the redox potential (ORP) in the region of zero encirclement.

As Eh-pH line chart, for example can use Pourbaix, the line chart of recording in M.Atlas of electrochemical equilibria in aqueous solutions.National Association of Corrosion Engineers. (1974) 644p..

As shown in Figure 1, Fe, Mn change according to the concentration of each composition in solution in solidified region simultaneously.For example, in solution, Fe concentration is 0.05M, in the situation that the Mn concentration in the Mn solution after stripping is 0.1M, in Fig. 1, can think that Fe is with 10 ⁰m and 10 ^-2between the line of M close 10 ^-2the border of M (the line * 1 of Fig. 1) is benchmark, and Mn is with 10 ⁰m and 10 ^-2the centre of the line of M is border (the line * 2 of Fig. 1).

In this case, preferably known, in Fig. 1, manganese form oxide compound and pH and the redox potential (ORP) of the region of solidification precipitation (in Fig. 1 with zero region surrounding) be approximately as shown in Figure 1 " pH:0.1 above and lower than 2.2 ", " redox potential (ORP): approximately+0.9V above and+below 1.2V ".

In addition, figure when Fig. 1 is 25 ℃ of water temperatures, in the situation that water temperature is different, as long as carry out temperature correction.As the method for revising, for example, by known method (, the balance multiplier correction based on Van ' t Hoff formula etc.), revise.

Therefore, the leach liquor (parting liquid) 10 containing manganese composition obtaining by solid-liquid separation process 6 is the in the situation that of above-mentioned Fe and Mn concentration, to this solution, add acid 12 pH is brought down below to 2.2, then, diffusion ozone redox potential (ORP) is increased to+more than 0.9V, thus, manganese forms oxide compound and solidification makes its precipitation.

Above-mentioned sour 12 is common acid, can use sulfuric acid, nitric acid, hydrochloric acid, other acid.In addition, diffusing capacity as ozone, preferably redox potential (ORP) limit diffusion ozone is observed on limit, according to redox potential (ORP), (for example reach set-point, in the temperature containing manganese leach liquor, it is 25 ℃, Fe in this leach liquor, Mn concentration are respectively in the situation of Fe:0.05M, Mn:0.1M, for+more than 1V) mode adjust.It should be noted that, the necessary amount of ozone changes according to the bubble footpath in device shape and when diffusion etc., therefore, can comparative costs etc. selects effective means.

It should be noted that, in above-mentioned insoluble operation 11, under the effect of the Mn oxide generating in the oxidation by manganese, in insoluble processing (being in ozone DIFFUSION TREATMENT) containing the leach liquor (parting liquid) 10 of manganese composition, become black, be difficult to distinguish that by naked eyes manganese oxidizing reaction carries out state.In the inadequate situation of manganese oxidizing reaction in insoluble operation 11, mn ion does not form solid and precipitates, and causes the deterioration of manganese recovery ratio.

On the other hand, if manganese oxidizing reaction is superfluous, the Mn oxide generating becomes the ion of superoxide and again dissolves, identical with dysoxidative situation, its result, and manganese recovery ratio worsens.For its reason, found that of inventor research, if manganese oxidizing reaction is superfluous, the oxide compound of manganese that becomes solid is further oxidized, and becomes the ion of manganese peroxide and be again dissolved in solution.

In Fig. 1, mainly there is superoxide (topmost in Fig. 1, the MnO of manganese ₄ ^-such material) ORP pH2 and+1.6V near, conventionally do not observe the rising of such ORP.But known, if manganese oxidizing reaction is superfluous, a part of Mn oxide becomes superoxide by the effect of ozone.Also known in addition, the generation of superoxide almost all forms oxide compound and carries out after solidification at manganese.

By these facts, need to differentiate the terminal of manganese oxidizing reaction.But, even if will manage by the reaction times terminal of manganese oxidizing reaction, in containing in the situations such as leach liquor (parting liquid) 10 of manganese composition by acquisitions such as Bioleachings, the composition of every part of leach liquor solution is sometimes also different, not necessarily limits and obtains the identical rate of recovery by the identical reaction times.In addition, in the situation that having considered to control by redox potential (ORP), also produce identical problem, be difficult to confirm clear and definite reaction end.

On the other hand, the solution that comprises manganese peroxide ion is red-violet colour.Therefore, the generation of the superoxide of the manganese in solution can easily be differentiated by observing the color of solution.Wherein, as previously described, in insoluble processing, under the coexisting of such Mn oxide (solid) particulate of the leach liquor (parting liquid) 10 containing manganese composition, the color that whole solution can become Mn oxide is black, cannot distinguish the variable color of solution.But, if leach liquor (parting liquid) the 10 separated Mn oxides containing manganese composition from insoluble processing can be observed the variation of the color of leach liquor, and then can judge the generation of the superoxide of manganese.

Therefore, in actual applications, preferably, in the insoluble operation 11 of being undertaken by ozone, take out termly or continuously the leach liquor (parting liquid) 10 containing manganese composition in insoluble processing, separated Mn oxide from the liquid taking out, the color of observing solution itself is differentiated the oxidizing reaction terminal of mn ion.

Particularly, take out the leach liquor (parting liquid) 10 containing manganese composition in insoluble processing, from the liquid taking out, the Mn oxide as solid is filtered, or standingly make its sedimentation etc. carry out separation, the color of observing filtrate or supernatant liquor, becomes the ruddy moment as the terminal of manganese oxidizing reaction using this color, finishes insoluble operation 11, so, can make manganese recovery ratio reach maximum value.

In addition, if allow at cost and during the relations such as space are set, by absorption photometric instrument, supernatant liquor is measured, thereby can be evaluated more objectively.Because manganese peroxide ion has maximum absorption wavelength near 525-545nm, therefore, due to the generation of manganese peroxide ion, the absorbancy under near wavelength 525-545nm can sharply increase.Thus, can determine objectively painted, the reaction end of supernatant liquor.

In actual applications, for the solution before ozone oxidation reaction, measure in advance near absorbancy 525-545nm, and by this absorbancy being made as to the rising multiplying power of the absorbancy in 1 situation, determine the terminal of the painted of supernatant liquor and reaction.

By described above, in the situation that differentiate the oxidizing reaction terminal of mn ion, in insoluble operation 11, separation can be for example set as shown in Fig. 2 (b), observe groove 19.In this case, for example from the reactive tank (not shown) of insoluble operation 11, take out on a small quantity, termly or continuously the leach liquor (parting liquid) 10 containing manganese composition in insoluble processing to separated, observe in groove 19, come precipitate and separate Mn oxide the color (color of ie in solution itself) of observing supernatant liquor by taken out liquid is standing.After observation, in order to improve manganese recovery ratio, also the Mn oxide after supernatant liquor and precipitate and separate can be returned in the reactive tank of insoluble operation 11.Wherein, the operation of supernatant liquor and/or Mn oxide being returned to reactive tank not necessarily.Can repeat to implement such operation until confirm the oxidizing reaction terminal (that is, until supernatant liquor becomes light red) of mn ion.

In addition, in above-mentioned, separated, observe in groove 19, to being undertaken by a small amount of leach liquor (parting liquid) 10 that contains manganese composition taking out in insoluble processing, standingly come the method for precipitate and separate Mn oxide to be illustrated.But, in the present invention, be not limited to the method for above-mentioned precipitate and separate, also can be by other method, leach liquor (parting liquid) 10 containing manganese composition in insoluble processing is separated with Mn oxide.For example, in separation, observation groove 19, also can filter the liquid taking out, the color of observing filtrate is differentiated the oxidizing reaction terminal of mn ion.Under these circumstances, after observation, in order to improve manganese recovery ratio, also the Mn oxide by filtrate and/or filtering separation can be returned in the reactive tank of insoluble operation 11.Wherein, the operation of filtrate and/or Mn oxide being returned in reactive tank not necessarily operates.

In addition, when the leach liquor (parting liquid) 10 containing manganese composition in taking out insoluble processing is observed its color, not necessarily need the solution taking out completely separated with Mn oxide.That is the degree of the color of the solution that, both separate stages also can be taken out for observable itself.

By above operation, be dissolved in containing the manganese in the leach liquor (parting liquid) 10 of manganese composition preferential insolublely and form solid, become most of iron ion (3 valency iron ions or also have divalent iron ion) and be dissolved in containing the state in the leach liquor (parting liquid) 10 of manganese composition.In ensuing recovery process 14, by the parting liquid 10 to after insoluble operation 11, carry out solid-liquid separation, reclaim the Mn oxide 15 of the high density after concentrating.It should be noted that, while carrying out solid-liquid separation, the solid-liquid separating method of use can be any means being selected from gravity settling separation, filtration, centrifugation, press filtration, membrane sepn etc.

On the other hand, reclaimed and in parting liquid 10a, be rich in iron ion (3 valency iron ions or also have divalent iron ion) after the recovery of Mn oxide 15.Therefore, in the present invention, parting liquid 10a in can passing through and in operation 16 and after reclaiming, and using it as treatment solution 4 recyclings that leaching operation 3 and use.

Send into and the recovery of operation 16 after parting liquid 10a by alkali 18, neutralize.For the alkali 18 neutralizing, can enumerate sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium bicarbonate etc.But, be not limited thereto.In addition, in and in operation 16, in order to prevent the concentrated of salt etc., preferably its part is discharged to outside system as discharging water 17.

Through in and after the recovery of operation 16, after parting liquid 10a, mix with the treatment solution 4 that leaches operation 3.So, 3 valency iron ions after reclaiming in parting liquid 10a are reduced into divalent iron ion by iron reducing bacteria contained in treatment solution 4, and this divalent iron ion works as the reductive agent of object being treated 1.According to mixing the present invention of object being treated 1 and iron reducing bacteria in the treatment solution 4 to comprising 3 valency iron ions, in arranging and operation 16 as the operation after recovery process 14, by by parting liquid 10a after the recovery through neutralization and the simple process that the treatment solution 4 that leaches operation 3 mixes, treatment solution can be recycled.In addition, by through in and when after the recovery of operation 16, parting liquid 10a mixes with the treatment solution 4 of leaching operation 3, the medium component except ferrous components is reduced by microbial consumption, therefore, can append as required new treatment solution.

As previously discussed, if by making the effect of iron reducing bacteria that 3 valency iron are reduced into divalent iron, and the object being treated that uses this divalent iron reduction to comprise manganese, can make manganese contained in object being treated at short notice and cheap and leaching simply.In addition, by separated residue the leach liquor leaching from manganese, and under acidic conditions, make ozone with separated after leach liquor effect, mainly make the preferential insoluble form precipitate and separate with Mn oxide of manganese reclaim manganese, meanwhile, can reuse (for example supernatant liquor) remaining leach liquor of isolating after precipitation.

That is, the treatment solution 4 using in leaching operation 3 is as the treatment solution that comprises 3 valency iron ions, and while mixing therein object being treated and iron reducing bacteria, and first, iron reducing bacteria reduces 3 valency iron ions in treatment solution, by the reaction (Fe of above-mentioned (ii) ³⁺+ e ^-→ Fe ²⁺) generation divalent iron.Then, in leaching operation 3, by the reaction (Fe of above-mentioned (i) ²⁺+ (" Mn oxide compound, oxyhydroxide etc. " or " MnO for example ₂, Mn ₂o ₃, Mn ₃o ₄") → Fe ³⁺+ Mn ²⁺) generate mn ion and 3 valency iron ions, obtain the leach liquor (leaching mud) 5 that contains mn ion and 3 valency iron ions.In addition, leach liquor (leaching mud) 5 is carried out to solid-liquid separation, in parting liquid 10 from solid-liquid separation, reclaim manganese, rear parting liquid 10a is reclaimed in neutralization, if it is mixed with the treatment solution 4 using in leaching operation 3, the reduction of the iron reducing bacteria in treatment solution 4 manganese reclaims 3 valency iron ions in parting liquid 10a, by the reaction (Fe of above-mentioned (ii) ³⁺+ e-→ Fe ²⁺) generation divalent iron ion.Manganese is reclaimed in above-mentioned by repeating (i) and reaction (ii), leach liquor can be recycled simultaneously.

So, the treatment solution 4 that employing is used in leaching operation 3 is as the treatment solution that comprises 3 valency iron ions, and mixing contains manganese therein object being treated and iron reducing bacteria while making method that mn ion leaches from object being treated, by in and leach liquor 10a after the recovery process 14 of 16 pairs of manganese of operation neutralize, then without special just process, can mix with the treatment solution 4 of leaching operation 3.

Embodiment

Below, by embodiment, the present invention will be described, but the present invention is not limited to following embodiment.

1) by iron reducing bacteria leaching of manganese

With the shown below object being treated that contains iron reducing bacteria, treatment solution, manganese, carry out.

< iron reducing bacteria >

Shewanella algae NBRC103173 strain

(NITE Biological information resources center)

< treatment solution >

To thering is the treatment solution that has added above-mentioned iron reducing bacteria in the solution of gradation composition of table 4 and obtained.

The concentration of amount of solution and iron reducing bacteria is as follows.

Amount of solution: 3000cm ³

Initial iron reducing bacteria concentration: 5 * 10 ¹³individual/m ³(5 * 10 ⁷individual/cm ³)

It should be noted that, " mineral solution " in table 4 is for having the mineral solution (Wolfe ' s Mineral Solution) of Wolfe of the gradation composition of table 5, and " vitamin solution " in table 4 is for having the vitamin solution (Wolfe ' s Vitamin Solution) of Wolfe of the gradation composition of table 6.

It should be noted that " the total amount 1000cm of the ion exchanged water in table 4,5,6 ³" refer to solution total amount is adjusted into 1000cm ³.

< object being treated >

Alkaline cell bits (manganese content: 32 quality %)

[table 4]

Material name	Addition
		Ironic citrate (III) trihydrate	16.7g(Fe：0.056mol)
Trisodium citrate dihydrate	10.3g(0.035mol)
		Peptone	0.5g
KCl	0.1g
		NH 4Cl	1.5g
NaH 2PO 4	0.6g
		Mineral solution (table 5)	10cm 3
Vitamin solution (table 6)	10cm 3
		Sodium.alpha.-hydroxypropionate	3.4g
Ion exchanged water	Total amount 1000cm 3

[table 5]

Material name	Addition
		Triacetamide	1.5g
MgSO 4·7H 2O	3.0g
		MnSO 4·H 2O	0.5g
NaCl	1.0g
		FeSO 4·7H 2O	0.1g
CoCl 2·6H 2O	0.1g
		CaCl 2	0.1g
ZnSO 4·7H 2O	0.1g
		CuSO 4·5H 2O	0.01g
AlK(SO 4) 2·12H 2O	0.01g
		H 3BO 3	0.01g
Na 2MoO 4·2H 2O	0.01g
		Ion exchanged water	Total amount 1000cm 3

[table 6]

Material title	Addition
		Bio	2.0mg
Folic acid	2.0mg
		Pyridoxine hydrochloride	10mg
Vitamin b1 hydrochloride	5.0mg
		Lin Suanna Vitamin B2 Sodium Phosphate (riboflavin)	5.0mg
Nicotine	5.0mg
		D-(+)-calcium pantothenate	5.0mg
Vitamin B12 (cyanocobalamin)	100μg
		Para-amino benzoic acid	5.0mg
Thioctic Acid (DL-α-Yeast Nucleic Acid)	5.0mg
		Ion exchanged water	Total amount 1000cm 3

In reaction vessel, mix above-mentioned treatment solution and object being treated, under following condition, carried out leaching and processed.

Sample (g)-treatment solution (cm ³) ratio of mixture: 22g/1000cm ³

The temperature for the treatment of solution: 25 ℃

The pH:7 for the treatment of solution

Treatment time: 24 hours

Atmosphere: anaerobic condition

During above-mentioned leaching is processed, the manganese leach liquor obtaining is sampled, with the membrane filter of 0.45 μ m, filter immediately.By ICP emission spectrometry method, to filtering the manganese concentration of the sample (filtrate) obtaining, carried out quantitatively.Take quantitative values as basis, calculate the manganese of leaching with respect to the ratio (leaching yield) of the manganese in object being treated, the results are shown in Fig. 3.

The manganese concentration of the filtrate after the leaching of 24 hours is processed is 0.1mol/1000cm ³, according to the present invention, as shown in Figure 3, obtained higher manganese the leaching yield ((0.1mol/1000cm of 80% left and right ³) ÷ (22g/1000cm ₃* 32 quality % ÷ Mn molecular weight 55g/mol) ≒ 80%).

2) by acid ozone DIFFUSION TREATMENT, reclaim manganese

For the manganese to from leach liquor is concentrated and purified, reclaim and test, use by 1) manganese leach liquor after the filtration of acquisition tests.By by 1) leach liquor that obtains moves in reactive tank, carries out under the following conditions ozone diffusion under sulfuric acid, and implement manganese and formed oxide compound and solidified experiment.

The amount of liquid of leach liquor (after filtering): 500mL

Ozone generating apparatus: EZ-OG-R4 (manufacture of Ecodesign company)

The agitator speed of reactive tank: 800rpm

Ozone generating apparatus electric current: electric current 3.8A

Ozone diffusing capacity: 1L/min

Use acid: sulfuric acid

Acid concentration: be changed to 3N by 0.1N

Ozone diffusion time: 150 minutes

After experiment, the membrane filter by 0.22 μ m filters, and solid is weighed for dry 3 days at 50 ℃ afterwards.

Filtrate, solid have all carried out quantitatively manganese concentration and concentration of iron by ICP emission spectrometry method.In addition, for solid, also by combustion ion chromatography, sulphur concentration has been carried out quantitatively.The results are shown in Fig. 4 and Fig. 5.

That in addition, the pH of the leach liquor for each sulfuric acid concentration (leach liquor before ozone DIFFUSION TREATMENT) is measured the results are shown in table 7.It should be noted that, in the situation that sulfuric acid concentration is higher, pH value is below zero.In the present embodiment, because the glass electrode formula pH determinator by common has been measured pH, therefore, in measurement result, not correct value be negative in the situation that, in table, recorded measured value.

[table 7]

The pH of sulfuric acid concentration leach liquor

W)

01172

03115

I038

2-006

3-027

Known as shown in Figure 4, the concentration of the sulfuric acid adding in order to make leach liquor become acidity is higher, and the containing ratio of the iron simultaneously precipitating with manganese reduces, the separated raising of manganese and iron.

Therefore in addition, for composition in addition, manganese composition is thought Manganse Dioxide, can think, remains the oxygen with manganese bonding, and due to the variation for fear of form, to have carried out low temperature dry for a long time, thereby also remain moisture.

Confirm in addition, in solid, also contain hardly the sulphur composition from the sulfuric acid adding in order to make leach liquor become acidity.

Can say in addition, be region more than 0.3N at sulfuric acid concentration, and the containing ratio of the iron in throw out is lower than 10%, and manganese can be separated well with iron.Under the condition that is 0.1N at sulfuric acid concentration, the iron being blended in throw out is more than 10%, has exceeded the initial target value of setting of the inventor, lower than 10%.

In addition, as shown in Figure 5, for manganese, with respect to more than 80% shifting as solid of the manganese amount in leach liquor.On the other hand, the manganese of filtrate side only detects lower than 1% with respect to the manganese amount in leach liquor.Think that remaining manganese is most of for reclaiming loss, in fact, with respect to almost 100% manganese solidification and shifting as solid of the manganese amount in leach liquor.It should be noted that, as the major cause that reclaims loss, think when manganese is become solid by ozone oxidation, with film like, be attached to reaction vessel first-class.

On the other hand, if be conceived to iron, sulfuric acid concentration is lower, and iron shifts and to improve for sedimentary ratio, and manganese and iron separated has inadequate tendency.Particularly, at sulfuric acid, add under the condition that concentration is 0.1N, more than 50% shifting as throw out of the iron in leach liquor, can not say the sufficient result of separation of iron.

3) discriminating (1) of the manganese oxidizing reaction terminal in acid ozone DIFFUSION TREATMENT

By by 1) leach liquor that obtains moves in reactive tank, limit is carried out sample edge to leach liquor and is carried out ozone diffusion, acid concentration is made as to 1N and ozone is made as to 190 minutes diffusion time, except these 3, with above-mentioned 2) under sulfuric acid, carry out ozone diffusion under identical condition, implemented to make manganese to form oxide compound and solidified experiment.

The sampling of leach liquor is carried out before ozone diffusion with in ozone DIFFUSION TREATMENT.In addition, the sampling in ozone DIFFUSION TREATMENT is carried out repeatedly with process ozone diffusion time simultaneously.When leach liquor is sampled, confirm that leach liquor fully stirs and becomes uniform state, sample respectively 50cm ³.Membrane filter by 0.22 μ m filters the leach liquor of sampling, isolates Mn oxide, has observed the color of filtrate (solution part).

In addition, utilize and above-mentioned 2) identical method, by the leach liquor sampling, measured manganese recovery ratio separately.Contained total manganese amount (quality) in the leach liquor of sampling before ozone diffusion is made as to 100%.

Before ozone diffusion, in the leach liquor of sampling, do not precipitate (solid).In addition, solid manganese is attached on reaction vessel with film like as mentioned above, quantitative generation error, therefore, the manganese concentration of the filtrate side of sample of take in the filtrate of sample before ozone DIFFUSION TREATMENT in manganese concentration and ozone DIFFUSION TREATMENT goes out manganese recovery ratio (quality base) as basic calculation.It should be noted that, the manganese concentration in filtrate has been undertaken quantitatively by ICP emission spectrometry method.

Experimental result is shown in to Fig. 6.

Fig. 6 represents that the color of filtrate and manganese recovery ratio are along with the variation of the process of ozone diffusion time.As shown in Figure 6, can think after ozonization soon, the organism in medium component leach liquor that results from has consumed ozone, does not produce the generation of Mn oxide.After about 100 minutes, start to generate Mn oxide, meanwhile, leach liquor has promptly become black.But, at this constantly, if filtered, removing Mn oxide, the color of having removed the filtrate (solution part) of Mn oxide becomes and is considered to result from the light yellow of medium component.In addition, if start to generate Mn oxide, along with the ozone process of diffusion time, simultaneously manganese recovery ratio rises rapidly at short notice, near ozone is 150 minutes diffusion time, reaches more than 99% manganese recovery ratio.

But ozone spread if keep original state to continue ozone diffusion time after 150 minutes, manganese recovery ratio reduces.Now, the color of filtrate become as the color of the superoxide of manganese red～red-violet colour.By these results, can draw following conclusion: in ozone diffusion time, after 150 minutes, generate the superoxide of manganese, manganese peroxidase becomes ion and is again dissolved in reaction solution, therefore, manganese recovery ratio reduces.

4) discriminating (2) of the manganese oxidizing reaction terminal in acid ozone DIFFUSION TREATMENT

As above-mentioned 3) experimental result as shown in, in acid ozone DIFFUSION TREATMENT, obtain high manganese recovery ratio aspect there is best ozone diffusion time.But best ozone is easily subject to diffusion time such as the impact of composition, reactor shape, bubble footpath, stirring velocity of reaction soln etc.Therefore, to predetermine best ozone diffusion time be extremely difficult for the manganese content of the kind based on iron reducing bacteria, object being treated, other acid ozone DIFFUSION TREATMENT condition (ozone diffusing capacity, acid concentration etc.).

Shown in table 8 is to carry out 4 following experiments and the result (batch No.1A～4A) that obtains, described experiment is as follows: ozone is made as to 150 minutes diffusion time, namely be made as by above-mentioned 3) ozone diffusion time of high manganese recovery ratio the best of obtaining, except this point, with above-mentioned 3) under sulfuric acid, carry out ozone diffusion under identical condition, make manganese form oxide compound and solidification.

In addition, meanwhile, measure the absorbancy under wavelength 525.5nm, obtained the ratio of the absorbancy of the solution when react beginning.

[table 8]

As shown in table 8, even if ozone diffusion time and other condition are identical, manganese recovery ratio also can be uneven, obtain surpass 99% rate of recovery only for the color of filtrate is ruddy " batch No.1A " once.The color of " batch No.2A, 3A " filtrate is light yellow, therefore, infers that the oxidizing reaction of manganese is insufficient.The color of " batch No.4A " filtrate is red-violet colour on the other hand, therefore, infers that the oxidizing reaction of manganese is carried out excessively.Now, the absorbancy under wavelength 525.5nm is measured, if get with ozone diffusion before the ratio of absorbancy of (0 minute), can confirm, owing to generating manganese peroxide ion, solution is colored, absorbancy increases according to its growing amount.During due to " batch No.1A ", generate manganese peroxide ion for trace, therefore, kept the higher rate of recovery, but in " batch No.4A ", the generation of manganese peroxide ion is superfluous, think that loss increases.As known from the above, for the ozone management of diffusion time, it is difficult making manganese recovery ratio stablize and reach maximum.

On the other hand, shown in table 9 is to carry out 4 following experiments and the result (batch No.1B～4B) that obtains, described experiment is as follows: the color of judgement filtrate becomes the ruddy moment for " manganese oxidizing reaction terminal " from light yellow, determine " ozone diffusion time ", except this point, with above-mentioned 3) under sulfuric acid, carry out ozone diffusion under identical condition, make manganese form oxide compound and solidification.That is, in this experiment, in the color of filtrate, from light yellow, become the ruddy moment and finish acid ozone DIFFUSION TREATMENT.

[table 9]

As shown in table 9, by being observed, the color of the filtrate of leach liquor determines manganese oxidizing reaction terminal (ozone diffusion time), can continue to obtain the rate of recovery that surpasses 99%.In addition, now, from the measurement result of absorbancy, in either case, all the generation of manganese peroxide ion is suppressed at lowlyer, can produce excessively or insufficiently and react, maximum thereby the rate of recovery reaches.

As narrated, owing to adopting the manganese oxidizing reaction of ozone to be subject to the impact of the composition, reactor shape, bubble footpath, stirring velocity etc. of reaction soln, therefore, in the identical reaction times (ozone diffusion time), may not obtain identical manganese recovery ratio above.Particularly, in use, utilized in the situation etc. of manganese leach liquor of microorganism, thought that the composition of leach liquor produces larger variation because of microbic activity and bacterium number etc., therefore, to the management in reaction times difficulty comparatively, unrealistic.On the other hand, even such as in the situation that the composition of leach liquor, because of larger variations of generation such as microbic activity and bacterium numbers, is observed the color of filtrate or supernatant liquor by taking out a small amount of leach liquor, also can stably obtain higher manganese recovery ratio.

5) restriction for the treatment of solution composition

First, use the shown below object being treated that contains iron reducing bacteria, treatment solution, manganese to carry out

Utilize the leaching of the manganese that iron reducing bacteria carries out.

< iron reducing bacteria >

Shewanella algae NBRC103173 strain

(NITE Biological information resources center)

< treatment solution >

Treatment solution A: added above-mentioned iron reducing bacteria and the treatment solution that obtains in the solution of gradation composition with table 4.

Treatment solution B: added above-mentioned iron reducing bacteria and the treatment solution that obtains in the solution of gradation composition with table 10.It should be noted that " the total amount 1000cm of the ion exchanged water in table 10 ³" refer to that being adjusted to solution total amount is 1000cm ³.

As the concentration of amount of solution and iron reducing bacteria, treatment solution A, B are as described below.

Amount of solution: 500cm ³

Initial iron reducing bacteria concentration: 5 * 10 ¹³individual/m ³(5 * 10 ⁷individual/cm ³)

In addition, " mineral solution " in table 4,10 is for having the mineral solution (Wolfe ' s Mineral Solution) of Wolfe of the gradation composition of table 5, and " vitamin solution " in table 4,10 is for having the vitamin solution (Wolfe ' s Vitamin Solution) of Wolfe of the gradation composition of table 6.

The carbon concentration and the phosphorus concentration that add in iron reducing bacteria treatment solution A, B are before undertaken quantitatively by full organic carbon instrument and high-frequency inductive coupling plasma body emission spectrometry (ICP emission spectrometry), as the concentration of each element in treatment solution.Quantitative result is shown in to table 11.

< object being treated >

The metallic dust (Mn:69 quality %, Fe:3 quality %) that refining procedure by iron work produces

[table 10]

Material name	Addition
		Ironic citrate (III) trihydrate	1.5g(Fe：0.005mol)
Trisodium citrate dihydrate	10.3g(0.035mol)
		Peptone	0.5g
KCl	0.1g
		NH 4Cl	1.5g
NaH 2PO 4	－
		Mineral solution (table 5)	10cm 3
Vitamin solution (table 6)	10cm 3
		Sodium.alpha.-hydroxypropionate	3.4g
Ion exchanged water	Total amount 1000cm 3

In reaction vessel, mix above-mentioned treatment solution and object being treated, under following condition, carried out leaching and processed.

Sample (g)-treatment solution (cm3) ratio of mixture: 5g/1000cm ³

The temperature for the treatment of solution: 25 ℃

The pH:7 for the treatment of solution

Treatment time: 24 hours

Atmosphere: the condition of being sick of

After above-mentioned leaching processing finishes, with the membrane filter of 0.45 μ m, resulting manganese leach liquor is filtered.In sample after filtration (filtrate), the concentration of contained manganese has been undertaken quantitatively by high-frequency inductive coupling plasma body emission spectrometry (ICP emission spectrometry).Quantitative result is shown in to table 11.

Then, use the manganese leach liquor after resulting filtration, by ozone DIFFUSION TREATMENT, carried out manganese recovery.It should be noted that, ozone DIFFUSION TREATMENT condition, except acid concentration being made as to this point of 1N, is made as and above-mentioned 2) identical condition, is spread and has been implemented to make manganese to form oxide compound and solidified processing by ozone.

After processing, with the membrane filter of 0.22 μ m, filter, solid is weighed for dry 3 days at 50 ℃ afterwards.

Then, solid is dissolved with acid, and by ICP emission spectrometry and carbon and sulfur analytical instrument, manganese, carbon and phosphorus are carried out quantitatively, quantitative thus manganese concentration, carbon concentration and the phosphorus concentration in solid.Quantitative result is shown in to table 11.

[table 11]

As shown in table 11, the carbon concentration and the phosphorus concentration that add in iron reducing bacteria treatment solution A, B are before as follows: in treatment solution A, be respectively 600mM, 5.2mM, be respectively 270mM, 0.16mM in treatment solution B.

In the situation that using treatment solution B leaching of manganese, the manganese concentration that leaches the leach liquor of processing after 24 hours is 42mM, has obtained more than 75% higher manganese leaching yield.In addition, as shown in table 11, the manganese leaching yield in the situation of use treatment solution B leaching of manganese is equal with the situation of use treatment solution A leaching of manganese.

In addition, the content of the manganese in the solid that comprises the manganese reclaiming by ozone DIFFUSION TREATMENT, carbon and phosphorus is manganese in the situation that having used treatment solution A: 45 quality %, carbon: 0.14 quality %, phosphorus: 0.8 quality %, on the other hand, in the situation that having used treatment solution B, be respectively manganese: 45 quality %, carbon: 0.07 quality %, phosphorus: 0.03 quality %, the containing ratio of carbon and phosphorus significantly reduces with respect to manganese containing ratio.

Claims (7)

1. a manganese recovery method, the method has following operation:

Leach operation, in the treatment solution that contains 3 valency iron ions, mix object being treated and the iron reducing bacteria that contains manganese, by described iron reducing bacteria, described 3 valency iron ions are reduced into divalent iron ion, take this divalent iron ion to leach into described treatment solution from described object being treated as reductive agent makes mn ion;

Solid-liquid separation process, the leach liquor that this leaching operation is obtained carries out solid-liquid separation;

Insoluble operation, makes it insoluble mn ion oxidation contained in parting liquid after this solid-liquid separation process; And

Recovery process, the manganese composition precipitate and separate that this insoluble operation is obtained and reclaiming.

2. manganese recovery method according to claim 1, wherein,

Using reclaimed the recovery that contains ferric ion of manganese composition from described parting liquid, parting liquid is as the treatment solution recycling of described leaching operation.

3. manganese recovery method according to claim 1 and 2, wherein,

Described insoluble operation is the parting liquid effect making under acidic conditions after ozone and described solid-liquid separation process, thus mn ion oxidation is made to its insoluble operation.

4. according to the manganese recovery method described in any one in claim 1～3, wherein,

Described object being treated is iron work by product and/or low grade ore and/or used battery and/or contains manganese powder dirt and/or contain manganese ore mud and/or contain manganese mud.

5. according to the manganese recovery method described in any one in claim 1～4, wherein,

In described insoluble operation, take out termly or continuously the liquid in insoluble processing, the colour-change of the solution part of the liquid that observation post takes out, differentiates the oxidizing reaction terminal of mn ion thus.

6. according to the manganese recovery method described in any one in claim 1～5, wherein,

Treatment solution in described leaching operation is the treatment solution that has limited carbon concentration and phosphorus concentration.

7. manganese recovery method according to claim 6, wherein,

Described carbon concentration is below 300mM, and described phosphorus concentration is below 0.5mM.

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