CN103620069B

CN103620069B - manganese recovery method

Info

Publication number: CN103620069B
Application number: CN201280031548.1A
Authority: CN
Inventors: 山口东洋司; 八尾泰子
Original assignee: NKK Corp
Current assignee: JFE Engineering Corp
Priority date: 2011-06-29
Filing date: 2012-06-28
Publication date: 2016-04-13
Anticipated expiration: 2032-06-28
Also published as: WO2013002416A1; CN103620069A; JP5229416B1; JP2014005496A

Abstract

The invention provides a kind of at an easy rate from low-grade mineral and containing the method reclaiming manganese manganese waste.The treated object and iron-reducing bacteria that contain manganese is mixed in containing the treatment solution of 3 valency iron ions, by described iron-reducing bacteria, described 3 valency iron ions are reduced into divalent iron ion, with this divalent iron ion for reductive agent makes mn ion leach into described treatment solution from described treated object, the leach liquor obtained is carried out solid-liquid separation, mn ion contained in parting liquid is mainly formed oxide compound and insoluble (solidification), then the manganese oxides precipitate obtained is separated and reclaims.

Description

Manganese recovery method

Technical field

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

Background technology

Specific valuable metal is reclaimed at present because the reason of cost also has difficulties from low-grade raw ore or refining steel or iron work by product.But, in recent years, due to the exhaustion of metals resources and the rising etc. of transaction value, need to reclaim valuable metal from such material.Such as, the manganese as one of valuable metal all becomes necessary metal in multiple fields of industrial community, and in the future, probably its demand will exceed reserve.

Particularly, in iron work, owing to consuming manganese in a large number as steelmaking feed, therefore, in ironmaking field, guarantee that the problem in manganese source is very severe.On the other hand, in iron work, more manganese is contained in a large amount of iron work by product such as dust, sludge, slag produced.Therefore, expect from iron work by product, to reclaim manganese and the technology that it can be used as steelmaking feed to recycle significantly eliminates the problems referred to above by establishing.

At this, as the method reclaiming valuable metal from mineral, known following method: mineral contacts with acid or the treatment solution of alkali, and valuable metal contained in dissolution of minerals also makes it leach in treatment solution, the valuable metal leached in this treatment solution by selecting neutralization and reclaiming.In addition, when reclaiming valuable metal from low-grade mineral, from the angle of cost, the general method adopting the leaching valuable metal carrying out from object mineral such as the acid that uses sulfuric acid to reclaim.

But reclaim for the method for valuable metal for acid such as use sulfuric acid etc. from object mineral as treatment solution, its cost is still very high, and 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 the recovery using acid, the more difficult leaching of manganese, the rate of recovery that there is a part of form reduce such problem.

On the other hand, also known following method: in making valuable metal ions from leaching of ores to treatment solution by using microorganism, thus reclaim valuable metal.According to the method, without the need to using a large amount of sulfuric acid etc. in can making valuable metal from leaching of ores to treatment solution, therefore, it is possible to reclaim valuable metal and can not the problems referred to above be caused from mineral.

In addition, as mentioned above, the method using microorganism to leach metal from mineral is called as Bioleaching method (Bioleaching), it is characterized in that, energy expenditure is 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.

Such as, following technology is proposed: make iron-reducing bacteria effect in patent documentation 1,3 valency Fe3+ reduction are become divalent iron, the metal (cobalt, nickel, manganese etc.) using described divalent iron to make to comprise in the group be made up of metal oxide and metal hydroxides leaches, generate leach liquor and residue, described leach liquor is separated with residue, reclaims the metal expected.Specifically, it is that leaching process substratum, iron-reducing bacteria and metal oxide or metal hydroxides are put into the technology that reactor carries out leaching process, more specifically, propose following technology: use step stirring-type reactor, stir culture base makes metal oxide etc. that sedimentation not occur on one side, while regulate the maximum pH leached in process to be less than 8.5, to be preferably neutral (such as below pH7.5), entirety is set to the leaching that preferred specific pH scope carries out metal.According to this technology, valuable metal (cobalt, nickel) contained in leach liquor can be reclaimed by known method, and use it for the purposes of expectation.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2007-113116 publication

Summary of the invention

The problem that invention will solve

But, in patent documentation 1, there is no concrete record about the method reclaiming valuable metal contained in leach liquor.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.

Namely, when the manganese contained by the technology proposed according to patent documentation 1 makes in treated object (metal oxide etc.) leaches, need to reclaim manganese from the leach liquor containing mn ion and iron ion (leaching when processing by carrying out being oxidized 3 valency iron of acquisition to divalent iron or also having not oxidized and remaining divalent iron).

As from containing the known method of metal being separated expectation in the leach liquor of many kinds of metal ions, in oriented leach liquor, add the method that medicament etc. carrys out optionally precipitate and separate metal kind.If apply the method to process the leach liquor comprising mn ion and iron ion, then in most cases, first, due to the precipitated separation of the iron ion easily producing insoluble salt, therefore, after needing that mn ion is remained in and being separated with iron in leach liquor, from leach liquor, manganese is separated.In such method, the recovery of manganese needs the separation circuit of twice, there is the problem that operation complicates.In addition, if from leach liquor precipitate and separate iron ion, be then difficult to iron-containing liquor (leach liquor) is recycled.

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, needing to add at leading portion the material forming complex compound with iron etc. makes iron dissolve in organic solvent, generally by being called that iron is separated to organic solvent layer from water layer extraction by the water/organic solvent of separatory, need the separation circuit residued in by the manganese of target in tank, and need to use a large amount of organic solvents.In addition, treatment process also increases, but also will consume huge electricity.In addition, the sorbing material used in absorption method usually costly, but also needs the disengaging after fractionation by adsorption, recovery process.Therefore, when wanting to reclaim manganese a large amount of treated objects such from iron work by product, if use electrolytic process and absorption method, then recovery cost is huge.

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

As mentioned above, according to the purposes of the manganese reclaimed, it is also important for fully reducing its foreign matter content, but in the prior art, not to reducing assorted Quality Research contained in the manganese of recovery.

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

The method of dealing with problems

The method of the present inventor to settlement separate target manganese conducts in-depth research, the treated object and iron-reducing bacteria that contain manganese is mixed in containing the treatment solution of 3 valency iron, make iron-reducing bacteria effect that 3 valency Fe3+ reduction are become divalent iron, the effect utilizing this divalent iron to be oxidized to 3 valency iron makes mn ion from leaching in treatment solution containing the treated object of manganese, the leach liquor leaching mn ion is carried out solid-liquid separation, manganese is reclaimed from the parting liquid after solid-liquid separation, now, target manganese carries out settlement separate by the state making solvability iron residue in parting liquid.Its result, finds by implementing given oxide treatment to parting liquid, makes mn ion contained in parting liquid mainly insoluble with the form of Mn oxide, thus can carry out precipitate and separate.

Fig. 1 is manganese in the aqueous solution of 25 DEG C and the redox potential (ORP) of iron and the state graph (Eh-pH figure) of pH.As shown in Figure 1, in Eh-pH figure, the region of manganese precipitation is almost consistent with the region that iron precipitates except the region surrounded with zero in FIG, and the region of iron precipitation is wider.Therefore, if (the having carried out ionization) region of all dissolving from manganese, iron makes redox potential (ORP), the state of pH changes, then in nearly all region, iron preferentially precipitates with the morphology solid of oxide compound or oxyhydroxide.But think, have only and in the region (region surrounded with zero in Fig. 1) of low pH, high ORP, to there is mainly manganese form oxide compound and solidification and the region of precipitation.

Therefore, the present inventor etc. expect, by the pH of the above-mentioned parting liquid containing mn ion and 3 valency iron ions and redox potential (ORP) being adjusted to pH and the redox potential (ORP) in the region (region surrounded with zero in Fig. 1) that mainly solidification also precipitates with manganese formation oxide compound in Eh-pH figure, the state of the iron ion being dissolved with the matrix as iron-reducing bacteria in liquid can be kept, mainly make manganese form oxide compound and make it insoluble and precipitate.

What the present inventor etc. studied further found that, by using acid reduce the pH of above-mentioned parting liquid and make ozone play a role to improve the ORP of above-mentioned parting liquid, from the above-mentioned parting liquid containing mn ion and 3 valency iron ions, manganese can be inexpensively and easily preferentially mainly made to form oxide compound and solidification.

In addition, contain 3 abundant valency iron ions in described parting liquid or also contain divalent iron ion further.Therefore, remain in parting liquid by making iron ion and precipitation of iron ions contained in above-mentioned parting liquid is not separated, above-mentioned parting liquid can be recycled as the treatment solution being used for making mn ion leach from treated object.

Finding in addition, by using specific iron-reducing bacteria that 3 valency Fe3+ reduction in treatment solution are become divalent iron, low-grade manganese contained in treated object can be leached at a high speed, efficiently.

In addition, the method to impurity (carbon, the phosphorus etc.) content reducing the final manganese reclaimed such as the present inventor is studied.

When employing Bioleaching method (Bioleaching) containing germy treatment solution, the Multiple components for the treatment of solution usually containing the Leaching reaction for promoting the metal utilizing iron-reducing bacteria.When the treatment solution containing iron-reducing bacteria, containing compositions such as 3 valency iron ions, electron donor, pH adjusting agent, pH buffer reagents.In addition, certainly also containing the necessary element grown for the iron-reducing bacteria made as microorganism, i.e. carbon, phosphorus.If these compositions are not enough, then iron-reducing bacteria cannot grow, its result, leaches metal and becomes difficulty.Therefore, usually according to the application target of Footwall drift and containing the composition (C, P etc.) that can be used as impurity in treatment solution.

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

The experiment obtaining described understanding is described.

First, ironic citrate (III) medium standard solution has been prepared as the treatment solution containing 3 valency iron.Containing carbon in the general composition of this ironic citrate (III) medium standard solution and ironic citrate (III), Trisodium Citrate, sodium formiate, in addition, containing phosphoric in SODIUM PHOSPHATE, MONOBASIC, in addition, carbon and phosphoric is contained in peptone.These elements are the essential component in the metal Leaching reaction utilizing iron-reducing bacteria to carry out, and the concentration (or content) of various composition 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 (or content) of above-mentioned various composition is the value in every 1L ironic citrate (III) medium standard solution.In addition, mM represents mmol/L.

At this, the present inventor etc. infer, and the carbon concentration in ironic citrate (III) medium standard solution (treatment solutions containing 3 valency iron) and phosphorus concentration can bring impact to the carbon concentration in the final manganese reclaimed and phosphorus concentration.To there is the treatment solution of the concentration (or content) of above-mentioned various composition as standard treatment solution, prepare to change three kinds of ironic citrate (III) medium standard solution of carbon concentration or phosphorus concentration as treatment solution relative to this standard treatment solution by following (A) ~ (C), 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 of standard treatment solution steps be down to 0g/L and the treatment solution (concentration: 0.6g/L, 0.3g/L, 0.1g/L, 0g/L totally 4 kinds) obtained.It should be noted that, the concentration (or content) of the composition beyond SODIUM PHOSPHATE, MONOBASIC is identical with standard treatment solution.In addition, measure the phosphorus concentration for the treatment of solution when being 0g/L by the concentration of SODIUM PHOSPHATE, MONOBASIC, result is 5mg/L (0.16mM).Think that it is from the composition beyond SODIUM PHOSPHATE, MONOBASIC.

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

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

Various ironic citrates (III) the medium standard solution (treatment solutions containing 3 valency iron) of above-mentioned (A) ~ (C) is added: 150cm in step stirred vessel ³, metallic dust (Mn:69 quality %, the Fe:3 quality %) 0.75g produced in refining procedure of iron work and iron-reducing bacteria shewanella algae(NBRC103173 strain): 1 × 10 ⁷individual/cm ³, the temperature of mixed solution is remained on about 30 DEG C, implements bubbling and the stirring of the 24 little nitrogen up to 144 hours, carried out leaching process.Then, gather leach liquor by solid-liquid separation, measure the Mn concentration in leach liquor and calculate Mn leaching yield.Their result is shown in table 1 ~ 3.

[table 1]

[table 2]

[table 3]

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

Table 2 has used the treatment solution of above-mentioned (B) to carry out to leach the result processed.As shown in table 2, if reduce the concentration of the ironic citrate (III) containing carbon component, then the manganese leaching yield at initial stage reduces.But, be 144 constantly little in the leaching treatment time, even if when the concentration of ironic citrate (III) trihydrate containing carbon component is reduced to 1.5g/L, also obtain the manganese leaching yield equal with standard treatment solution situation.

Table 3 has used the treatment solution of above-mentioned (C) to carry out to leach the result processed.If reduce the concentration of the Trisodium Citrate containing carbon component, then manganese leaching yield significantly reduces, and leach the treatment time even if extend, leaching yield is also still very low.That is, can say, consider from manganese leaching yield viewpoint, preferably do 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.

Ironic citrate (III) trihydrate concentration in treatment solution is set to 1.5g/l (5mM), carbon concentration in treatment solution when Trisodium citrate dihydrate concentration being set to 10.3g/L (35mM) is 270mM.

In addition, the present inventor etc. carry out experiment similar to the above repeatedly, measure the impurity concentration (carbon concentration and phosphorus concentration) of the final manganese reclaimed.It found that, if the carbon concentration in treatment solution is limited in below 300mM, phosphorus concentration is limited in below 0.5mM, then the impurity concentration of the final manganese reclaimed 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, the treated object and iron-reducing bacteria that contain manganese is mixed in containing the treatment solution of 3 valency iron ions, by described iron-reducing bacteria, described 3 valency iron ions are reduced into divalent iron ion, with this divalent iron ion for reductive agent makes mn ion leach into described treatment solution from described treated object;

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

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

Recovery process, the manganese components settle this insoluble operation obtained is separated and reclaims.

[2] the manganese recovery method described in above-mentioned [1], wherein, will reclaim recycling containing the treatment solution of parting liquid after the recovery of ferric ion as described leaching operation of manganese composition from described parting liquid.

[3] above-mentioned [1] or the manganese recovery method described in [2], wherein, described insoluble operation is the parting liquid effect after making ozone and described solid-liquid separation process in acid condition, the operation making it insoluble mn ion oxidation thus.

[4] the manganese recovery method according to any one of above-mentioned [1] ~ [3], wherein, described treated object 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 according to any one of above-mentioned [1] ~ [4], wherein, in described insoluble operation, take out the liquid in insoluble process termly or continuously, observe the colour-change of the solvent portions of the liquid taken out, differentiate the oxidizing reaction terminal of mn ion thus.

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

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

The effect of invention

According to manganese recovery method of the present invention, can carry out concentrated with higher enrichment factor under the more stable condition that manganese class contained in manganese mineral etc. is such under room temperature, normal atmosphere and reclaim, simultaneously, by Reusability treatment solution, the expense that manganese reclaims can be reduced, industrially play significant effect.In addition, manganese recovery method of the present invention owing to inexpensively and easily can reclaim manganese from a large amount of treated objects, and therefore, particularly, the method reclaiming manganese in the iron work by product as generation a large amount of from iron work is very effective.

Accompanying drawing explanation

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

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

Fig. 3 illustrates that the figure of the manganese leaching yield of the embodiment of bits pulverized by the discarded drying battery of test.

Fig. 4 illustrates the figure of composition in solid when carrying out ozone diffusion to the manganese leach liquor of embodiment in acid condition.

Fig. 5 illustrates the figure in acid condition the manganese leach liquor of embodiment being carried out to manganese recovery ratio when ozone spreads.

Fig. 6 is the figure of the change that manganese recovery ratio when carrying out ozone DIFFUSION TREATMENT to manganese leach liquor of the present invention in acid condition and filtrate color are shown.

Nomenclature

1 ... treated object

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 ... containing the leach liquor (parting liquid) of 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 ... be separated, observe groove

Embodiment

Below, the present invention is described in detail.

The feature of manganese recovery method of the present invention is, the method has following operation: leach operation, the treated object and iron-reducing bacteria that contain manganese is mixed in containing the treatment solution of 3 valency iron ions, by described iron-reducing bacteria, described 3 valency iron ions are reduced into divalent iron ion, with this divalent iron ion for reductive agent makes mn ion leach into described treatment solution from described treated object; Solid-liquid separation process, carries out solid-liquid separation by the leach liquor that this leaching operation obtains; Insoluble operation, makes it insoluble mn ion contained in parting liquid after this solid-liquid separation process oxidation; And recovery process, the manganese components settle this insoluble operation obtained is separated and reclaims.In addition, parting liquid after the recovery comprising the 3 valency iron ions having reclaimed manganese composition from above-mentioned parting liquid also can be recycled in above-mentioned leaching operation.

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 treated object 1 containing manganese is pulverized by broken process 2.Then, in leaching operation 3, by the mixing of treated object 1, treatment solution 4 containing 3 valency iron ions and iron-reducing bacteria, obtain leaching mud (leach liquor) 5.In this leaching operation 3, by iron-reducing bacteria, 3 valency iron ions being reduced into divalent iron ion, meanwhile, by making this divalent iron ion to the manganese composition effect in treated object 1, making the manganese component dissolves in treated object 1.

As treated object 1, be the material containing manganese, such as, can use 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 treated object 1, except containing except the solid of manganese, can also enumerate containing manganese powder dirt and/or containing manganese ore mud and/or containing manganese mud etc.

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

In addition, as the manganese composition comprised in treated object 1, MnO can be enumerated ₂, Mn ₂o ₃, Mn ₃o ₄deng.

Treated object 1 is by for mixing with treatment solution 4 and making mn ion leach into leaching operation 3 in treatment solution 4.But if comparatively large at the particle diameter to the treated object 1 leaching the stage that operation 3 shifts, then specific surface area reduces, and solid-liquid contact area (contact area of treated object 1 and treatment solution 4) reduces, and leaching velocity reduces.In addition, when use intermittent reaction container carries out leaching operation 3, if also worry that the particle diameter of treated object 1 is comparatively large, the treated object 1 meeting sedimentation when leaching process, thus leaching process can not be carried out fully.

Due to above reason, in the present invention, when treated object 1 is solid, to reduce particle diameter to improve, for the purpose of the reaction efficiency in leaching operation 3, broken process 2 is preferably set.Particle diameter is less, and reaction efficiency more improves, and more can shorten and leach the reaction times in operation 3.Therefore, in the present invention, preferably make the particle diameter to the treated object 1 leaching the stage that operation 3 shifts be below 100mm, be more preferably less than 100 μm.But, from the viewpoint of the complexity of solid-liquid separation, preferably the particle diameter of treated object 1 is set to more than 1 μm.

As breaking method, jaw crusher can be used, rotate the known breaking methods such as grinding machine.In addition, when the particle diameter of treated object 1 is enough little, also broken process 2 can be omitted.

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

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

At this, as treatment solution 4, the treatment solution that with the addition of divalent iron ion also can be used.But, in the present invention, preferably, use the treatment solution comprising 3 valency iron ions, treated object and iron-reducing bacteria is mixed in this treatment solution, above-mentioned 3 valency iron ions are reduced into divalent iron ion, meanwhile, as reductive agent, mn ion are leached into treatment solution 4 from treated object 1 this divalent iron ion.

Iron-reducing bacteria to be given and accepted electronics by supply iron breathing as 3 valency iron ions of electron acceptor and the bacterium that grows from electron donor (organism etc.), and it has the effect by the reaction of following (ii), 3 valency Fe3+ reduction being become divalent iron.

Fe ^3＋＋e ^-→Fe ^2＋…(ii)

Therefore, if mix treated object 1 and iron-reducing bacteria in the treatment solution comprising 3 valency iron ions, then iron-reducing bacteria uses 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 comprising divalent iron and iron-reducing bacteria.Because the divalent iron generated by the reaction of above-mentioned (ii) contributes to the reaction of above-mentioned (i), therefore, mn ion can be made to leach in treatment solution 4 in leaching operation 3.

As 3 valency iron and the iron-reducing bacteria used in the present invention, the bacterium of kind shown below can be enumerated.In addition, the iron simultaneously adding iron-reducing bacteria in the treatment solution comprising 3 valency iron ions breathe needed for 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 following shown acid, alkali, pH adjusting agent, the pH for the treatment of solution is adjusted to given pH described later.In addition, certainly need to exist simultaneously and make the element etc. necessary to the growth of iron-reducing bacteria.

< iron-reducing bacteria >

As the iron-reducing bacteria used in leaching operation 3 of the present invention, include, for example geobacter metallireducenslovleyetal. (ATCC53774, DSM7210), desulfomonaspalmitatiscoatesetal. (ATCC51701, DSM12931), desulfuromusakysingiiliesack & Finster (DSM7343), pelobactervenetianusschink & Stieb (DSM2395), shewanellaalgaeshimiduetal.1990 (NBRC103173, IAM14159, ATCC51181), ferrimonasbalearicarossello-Moraetal. (DSM9799), aeromonashydrophilasubsp. hydrophila(Chester) Stanier (DSM30014), sulfurospirillumbarnesiistolzetal. (ATCC700032, DSM10660), wolinellasuccinogenes(Wolinetal.) Tanneretal. (DSM1740, ATCC29543), desulfovibriodesulfuricanssubsp. desulfuricans(Beijerinck) Kluyver & vanNiel (DSM642, ATCC29577), geothrixfermentanscoatesetal. (ATCC700665), deferribacterthermophilusgreeneetal. (DSM14813), thermotogamaritimestetter & Huber (DSM3109) etc.

In addition, also can use Fe3+ reduction archeobacteria in the present invention, as Fe3+ reduction archeobacteria, include, for example archaeoglobusfulgidusstetter (ATCC49558, DSM4304), pyrococcus furiosusfiala & Setter (ATCC49587, DSM3638), pyrodictiumabyssiPleyandStetter (ATCC49828, DSM6158), methanothermococcusthermolithotrophicus(Huberetal.) Whitman (DSM2095, JCM10549, ATCC35097) etc.

At this, for above-mentioned iron-reducing bacteria, Fe3+ reduction archeobacteria, although describe 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 belonging to 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, bacterial strain preserves office, the title of facility is expressed as follows the meaning respectively.

ATCC：AmericanTypeCultureCollection，Manassas，VA，USA

DSM：DeutscheSammlungvonMikroorganismenundZellkulturenGmbH(DSMZ)，Braunschweig，Germany

NBRC：NITEBiologicalResourceCenter，Chiba，Japan

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

JCM, IAM:JapanCollectionofMicroorganisms, RIKEN, Saitama, Japan [(solely) RIKEN Biological Resource Center microbial material exploitation room (RIKEN's バイオリソースセンター microorganism Cai Liao development room) (JCM)]

As iron-reducing bacteria, from the viewpoint of open air process complexity, preferred facultative anaerobic bacteria.Such as, in above-mentioned bacterial classification, the bacterium recorded as iron-reducing bacteria can be enumerated.

In addition, as iron-reducing bacteria, from the viewpoint of open air process complexity, preferably on the bacterium of normal temperature region growing.Such as, in above-mentioned bacterial classification, the bacterium (except Geothrixfermentans and Thermotogamaritime) recorded as iron-reducing bacteria can be enumerated.

In addition, as iron-reducing bacteria, preferred Geobactermetallireducens or Shewanellaalgae, more preferably Shewanellaalgae.

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

< 3 valency iron ion >

The 3 valency iron ions used 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, such as ironic citrate (III), ironic formiate (III), ironic acetate (III) etc. can be enumerated.

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

< electron donor >

Electron donor suitably can be selected according to above-mentioned iron-reducing bacteria.Such as when iron-reducing bacteria is Geobactermetallireducens or Shewanellaalgae, organism can be used as electron donor.

As above-mentioned organism, include, for example organism [carboxylate salt (the fat formula carboxylate salt (soap): formate, acetate etc. of 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 (toluenephenol) etc.)] etc.In addition, as above-mentioned organism, except comprising carbon, hydrogen, oxygen, such as nitrogen, sulphur, other element can certainly be comprised.In addition, as above-mentioned organism, be not limited to organism that is water-soluble or water dispersible, also can comprise neither water-soluble neither the organic particulate of water dispersible.

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

< acid, alkali, pH adjusting agent >

Can add in above-mentioned treatment solution 4 be selected from acid, alkali, pH adjusting agent more than one pH for the treatment of solution 4 is adjusted to given pH described later.

Above-mentioned acid is not particularly limited, can the organic acids such as mineral acid, formic acid, acetic acid, lactic acid, citric acid, succsinic acid, oxysuccinic acid such as example example hydrochloric acid, 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, carrying out pH and may change with reaction.Therefore, also can add above-mentioned pH adjusting agent and/or pH buffer reagent suitably adjusts pH, suppress change.

As long as the pH buffer reagent added to above-mentioned treatment solution 4 has the buffer reagent of surge capability at neutral pH range, be not particularly limited, such as acetic acid/sodium acetate can be enumerated, 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 added in above-mentioned treatment solution 4, the buffer reagent that can play a role as above-mentioned electron donor can be used.At iron-reducing bacteria be such as shewanellaalgaewhen, lactic acid/Sodium.alpha.-hydroxypropionate etc. can be used as pH buffer reagent and plays a role, and also can play a role as electron donor simultaneously.In addition, as the pH buffer reagent added in above-mentioned treatment solution 4, the buffer reagent that can form complex compound with the mn ion leached from treated object 1 can be used.Such as, citric acid/sodium citrate etc. can with Mn ²⁺form complex compound.

It should be noted that, not damaging object of the present invention and do not damage in the scope of pH shock absorption, above-mentioned pH buffer reagent can be used alone one or is used in combination of two or more with arbitrary content.

＜pH＞

There is some difference according to bacterial classification or bacterial strain difference in the iron-reducing bacteria used in the present invention, but its growth optimal pH is in neutral pH range.But in leaching operation 3, the pH carrying out treatment solution 4 with reaction likely changes.

Therefore, as long as the pH of above-mentioned treatment solution 4 is just not particularly limited near 7.0.But, when the pH for the treatment of solution 4 changes, by control more than 5.0 and less than 9.0, preferably control to be more than 6.0 and less than 8.0, preferably control to be more than 6.5 and less than 7.5 further, thus, efficient leaching can be realized.

In addition, according to the purposes reclaiming manganese, require the impurity reduced as far as possible in this manganese.Such as when using recovery manganese as steelmaking feed, in order to anti-blocking, phosphorus being mixed into cast steel, require highly purified recovery manganese.

In manganese recovery method of the present invention, in the carbon concentration reduced in the final manganese reclaimed and phosphorus concentration, preferably above-mentioned treatment solution 4 is made the treatment solution limiting carbon concentration and phosphorus concentration.That is, its composition is preferably regulated to make carbon concentration and phosphorus concentration in the composition adding the treatment solution before iron-reducing bacteria be below certain value.

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

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

When implementing when using above-mentioned such treatment solution 4 to leach operation 3, under the state intercepting oxygen, treated object 1 is made to contact with treatment solution 4 and mix.Its reason is, if there is oxygen, then worries 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 DEG C.It should be noted that, extraction time changes according to leaching condition, but is generally 24 ~ 72 hours.

As mentioned above, if treated object 1, iron-reducing bacteria and the treatment solution 4 that comprises 3 valency iron ions mixed, then 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 treated object 1, divalent iron is oxidized to 3 valency iron, simultaneously, manganese in treated object 1 leaches in treatment solution 4, thus obtains the leaching mud (leach liquor) 5 comprising mn ion and 3 valency iron ions or also comprise unreacted divalent iron ion further.The leaching mud (leach liquor) 5 obtained by leaching operation 3 is sent to solid-liquid separation process 6.

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

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

The solid-liquid separating method used in solid-liquid separation process 6 can for being selected from any means in gravity settling separation, filtration, centrifugation, press filtration, membrane sepn etc.In addition, when the solids concn leaching mud 5 is higher, preferably press filtration is used.

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, the solidity composition outside the demanganization mainly comprising iron-reducing bacteria, treated object 1 in residue (solid) 7.

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 residue 9, meanwhile, a part is reclaimed (with reference to Fig. 2 (a)) as unreacted residue 8.

In insoluble operation 11, given insoluble process is implemented to the leach liquor (parting liquid) 10 containing manganese composition obtained by solid-liquid separation process 6, form oxide compound by being adjusted to manganese containing the pH of leach liquor (parting liquid) 10 of manganese composition and redox potential (ORP) and making its insoluble (solidification) and precipitate but the region do not precipitated of iron, namely in Eh-pH figure (Fig. 1) by the pH in region of zero encirclement and redox potential (ORP).Thus, be dissolved in preferentially insoluble containing the manganese in the leach liquor 10 of manganese composition and form solid.This insoluble operation 11 is preferably set to the operation making ozone act on the leach liquor (parting liquid) 10 containing manganese composition in acid condition, such as, preferably add after sour 12, by ozone generating apparatus 13 diffused ozone in containing the leach liquor (parting liquid) 10 of manganese composition.Namely, preferably by adding the pH that sour 12 regulate the leach liquor (parting liquid) 10 containing manganese composition, spread the redox potential (ORP) of the leach liquor (parting liquid) 10 regulated containing manganese composition by ozone simultaneously, thus, form oxide compound and solidification by being adjusted to manganese containing the pH of leach liquor 10 of manganese composition and redox potential (ORP) and precipitating but the non-setting region of iron, namely in Eh-pH figure (Fig. 1) by the pH in region of zero encirclement and redox potential (ORP).

As Eh-pH line chart, such as Pourbaix can be used, the line chart recorded in M.Atlasofelectrochemicalequilibriainaqueoussolutions.Nat ionalAssociationofCorrosionEngineers. (1974) 644p..

As shown in Figure 1, Fe, Mn change according to the concentration of each composition in solution in solidified region simultaneously.Such as, Fe concentration is 0.05M in the solution, when the Mn concentration in the Mn solution after stripping is 0.1M, in FIG, can think that Fe is with 10 ⁰m and 10 ^-2between the line of M close 10 ^-2the border (the line * 1 of Fig. 1) of M 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, manganese forms oxide compound and solidification and the pH of the region of precipitation (with the region of zero encirclement in Fig. 1) and redox potential (ORP) are approximately " more than pH:0.1 and lower than 2.2 ", " redox potential (ORP): about more than+0.9V and below+1.2V " as shown in Figure 1.

In addition, figure when Fig. 1 is water temperature 25 DEG C, when water temperature is different, as long as carry out temperature adjustmemt.As the method revised, undertaken revising by known method (such as, based on the balance multiplier correction etc. of Van ' tHoff formula).

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

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

It should be noted that, in above-mentioned insoluble operation 11, under the effect of the Mn oxide generated in the oxidation by manganese, in insoluble process, the leach liquor (parting liquid) 10 containing manganese composition of (namely in ozone DIFFUSION TREATMENT) becomes black, is difficult to distinguish that manganese oxidizing reaction carries out state by naked eyes.Manganese oxidizing reaction in insoluble operation 11 is insufficient, 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, then the Mn oxide generated 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 the present inventor's research, if manganese oxidizing reaction is superfluous, then the oxide compound becoming the manganese of solid is oxidized further, and becomes the ion of manganese peroxide and be again dissolved in solution.

In FIG, mainly there is superoxide (topmost in Fig. 1, the MnO of manganese ₄ ^-such material) ORP near+1.6V, usually do not observe the rising of such ORP at pH2.But known, if manganese oxidizing reaction is superfluous, then 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 at manganese and carries out after solidification.

True by these, need the terminal differentiating manganese oxidizing reaction.But, even if the terminal of manganese oxidizing reaction will be managed by the reaction times, in the situations such as the leach liquor (parting liquid) 10 containing manganese composition obtained by Bioleaching etc., the composition of every part of leach liquor solution is sometimes also different, is not necessarily defined through the identical reaction times to obtain the identical rate of recovery.In addition, also produce identical problem when considering and being controlled by redox potential (ORP), be difficult to confirm clear and definite reaction end.

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

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

Specifically, take out the leach liquor (parting liquid) 10 containing manganese composition in insoluble process, from the liquid taken out, the Mn oxide as solid is filtered, or leaving standstill makes its sedimentation etc. be separated, observe the color of filtrate or supernatant liquor, this color is become the terminal of ruddy moment as manganese oxidizing reaction, terminate insoluble operation 11, so, manganese recovery ratio can be made to reach maximum value.

In addition, if allow in the relation such as cost and installation space, then by absorption photometric instrument, supernatant liquor is measured, thus can evaluate 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 the wavelength near 525-545nm can sharply increase.Thus, painted, the reaction end of supernatant liquor can be determined objectively.

In actual applications, the absorbancy near 525-545nm is measured in advance for the solution before ozone oxidation reaction, and the rising multiplying power of absorbancy when by this absorbancy being set to 1 determines the terminal of the painted of supernatant liquor and reaction.

By described above, when differentiating the oxidizing reaction terminal of mn ion, in insoluble operation 11, separation such as can be set as shown in Fig. 2 (b), observe groove 19.In this case, the leach liquor (parting liquid) 10 containing manganese composition such as on a small quantity, termly or continuously from the reactive tank (not shown) of insoluble operation 11 in the insoluble process of taking-up is in separation, observation groove 19, taken out liquid is left standstill precipitate and separate Mn oxide, and observes the color (color of ie in solution itself) of supernatant liquor.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, supernatant liquor and/or Mn oxide are returned the operation of 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, be separated, observing in groove 19, the method leaving standstill precipitate and separate Mn oxide by a small amount of leach liquor (parting liquid) 10 containing manganese composition taken out in insoluble process is being illustrated.But, in the present invention, be not limited to the method for above-mentioned precipitate and separate, also by other method, the leach liquor (parting liquid) 10 containing manganese composition in insoluble process can be separated with Mn oxide.Such as, in separation, observe in groove 19, also can filter the liquid taken out, the color of observing filtrate differentiates 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 that filtrate and/or Mn oxide return in reactive tank is not necessarily operated.

In addition, when taking out the leach liquor (parting liquid) 10 containing manganese composition in insoluble process and observing its color, not necessarily need the solution of taking-up to be separated completely with Mn oxide.That is, both separate stages also can be the degree of the color of the solution of observable taking-up itself.

By above operation, be dissolved in preferentially insoluble containing the manganese in the leach liquor (parting liquid) 10 of manganese composition and form solid, becoming most of iron ion (3 valency iron ions or in addition 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 carrying out solid-liquid separation to the parting liquid 10 after insoluble operation 11, reclaim the Mn oxide 15 of the high density after concentrating.It should be noted that, the solid-liquid separating method carrying out use during solid-liquid separation can be selected from any means in gravity settling separation, filtration, centrifugation, press filtration, membrane sepn etc.

On the other hand, iron ion (3 valency iron ions or in addition divalent iron ion) is rich in after having reclaimed the recovery of Mn oxide 15 in parting liquid 10a.Therefore, in the present invention, with parting liquid 10a rear with recovery in operation 16 in can passing through, and the treatment solution 4 leaching operation 3 use is it can be used as to recycle.

In feeding and operation 16 recovery after parting liquid 10a neutralized by alkali 18.Alkali 18 for 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 discharge water 17.

Through in and operation 16 recovery after mix with the treatment solution 4 leaching operation 3 after parting liquid 10a.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 treated object 1.According to the present invention mixing treated object 1 and iron-reducing bacteria in the treatment solution 4 comprising 3 valency iron ions, arrange with operation 16 as the operation after recovery process 14, by the simple process that parting liquid 10a after the recovery of neutralization is mixed with the treatment solution 4 leaching operation 3, treatment solution can be recycled.In addition, by through in and operation 16 recovery after parting liquid 10a with leaching operation 3 treatment solution 4 mix time, the medium component except ferrous components is reduced by microbial consumption, therefore, can add new treatment solution as required.

As previously discussed, if by making iron-reducing bacteria effect that 3 valency Fe3+ reduction are become divalent iron, and use this divalent Fe3+ reduction to comprise the treated object of manganese, then can to make in treated object contained manganese at short notice and cheap and leach simply.In addition, residue is separated by the leach liquor that leaches from manganese, and the leach liquor effect after making ozone in acid condition and being separated, mainly make manganese preferentially insoluble with the form precipitate and separate of Mn oxide to reclaim manganese, meanwhile, (such as supernatant liquor) the remaining leach liquor after isolating precipitation can be reused.

Namely, to the treatment solution 4 of use in operation 3 be leached as the treatment solution comprising 3 valency iron ions, and when mixing treated object and iron-reducing bacteria wherein, first, 3 valency iron ions in iron-reducing bacteria reduction treatment liquid, by the reaction (Fe of above-mentioned (ii) ³⁺+ e ^-→ Fe ²⁺) generate divalent iron.Then, in leaching operation 3, by the reaction (Fe of above-mentioned (i) ²⁺+ (" Mn oxide compound, oxyhydroxide etc. " or " such as MnO 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 containing mn ion and 3 valency iron ions.In addition, solid-liquid separation is carried out to leach liquor (leaching mud) 5, manganese is reclaimed from the parting liquid 10 after solid-liquid separation, rear parting liquid 10a is reclaimed in neutralization, if it is mixed with the treatment solution 4 used in leaching operation 3, iron-reducing bacteria reduction manganese then in treatment solution 4 reclaims 3 valency iron ions in parting liquid 10a, by the reaction (Fe of above-mentioned (ii) ³⁺+ e-→ Fe ²⁺) generate divalent iron ion.Reclaim manganese by the reaction repeating above-mentioned (i) and (ii), leach liquor can be recycled simultaneously.

So, adopt using leach the treatment solution 4 that uses in operation 3 as comprise the treatment solution of 3 valency iron ions and the treated object of mixing wherein containing manganese and iron-reducing bacteria mn ion is leached from treated object method time, by in and operation 16 pairs of manganese recovery process 14 after leach liquor 10a neutralize, then without the need to especially process just can with leaching operation 3 treatment solution 4 in mix.

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

The treated object containing iron-reducing bacteria, treatment solution, manganese shown below is used to carry out.

< iron-reducing bacteria >

ShewanellaalgaeNBRC103173 strain

(NITE Biological Resource Center)

< treatment solution >

To have table 4 gradation composition solution in the addition of above-mentioned iron-reducing bacteria and the treatment solution 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, for having the Mineral Solution (Wolfe ' sMineralSolution) of the Wolfe of the gradation composition of table 5, " vitamin solution " in table 4 is for having the vitamin solution (Wolfe ' sVitaminSolution) of the 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 to 1000cm ³.

< treated object >

Alkaline cell bits (Fe 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 treated object, carried out under the following conditions leaching process.

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

The temperature for the treatment of solution: 25 DEG C

The pH:7 for the treatment of solution

Treatment time: 24 hours

Atmosphere: anaerobic condition

In above-mentioned leaching process, the manganese leach liquor obtained is sampled, filters with the membrane filter of 0.45 μm immediately.Carry out quantitatively by ICP emission spectrometry method to filtering the manganese concentration of sample (filtrate) obtained.Based on quantitative values, calculate the ratio (leaching yield) of manganese relative to the manganese in treated object of leaching, result is shown in Fig. 3.

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

2) manganese is reclaimed by acid ozone DIFFUSION TREATMENT

In order to concentrated and purified to the manganese from leach liquor, reclaim and test, use by 1) manganese leach liquor after the filtration that obtains tests.By by 1) leach liquor that obtains moves in reactive tank, carries out ozone diffusion under the following conditions under sulfuric acid, and implement manganese and form 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, by the membrane filter of 0.22 μm, solid is weighed after dry 3 days at 50 DEG C.

Filtrate, solid are 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 to be carried out quantitatively.Result is shown in Fig. 4 and Fig. 5.

In addition, the result that the pH of the leach liquor (leach liquor before ozone DIFFUSION TREATMENT) for each sulfuric acid concentration carries out measuring is shown in table 7.It should be noted that, when sulfuric acid concentration is higher, pH value is less than zero.In the present embodiment, owing to determining pH by common glass electrode formula pH determinator, therefore, not correct value when measurement result is negative, in table, describe 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 added to make leach liquor become acid is higher, and the containing ratio of the iron simultaneously precipitated with manganese reduces, and manganese is separated raising with iron.

In addition, for composition in addition, manganese composition thinks Manganse Dioxide, therefore can think, remains the oxygen with manganese bonding, and carried out low temperature due to the change in order to avoid form dry for a long time, thus also remains moisture.

Confirm in addition, also hardly containing the sulphur composition from the sulfuric acid added to make leach liquor become acid in solid.

Can say in addition, be the region of 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.Be under the condition of 0.1N at sulfuric acid concentration, the iron be mixed in throw out is more than 10%, the target value set at first beyond the present inventor, namely lower than 10%.

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

On the other hand, if be conceived to iron, then sulfuric acid concentration is lower, and iron transfer improves for sedimentary ratio, and manganese is separated insufficient tendency with iron.Particularly, add under concentration is the condition of 0.1N at sulfuric acid, more than 50% transfer of the iron in leach liquor is throw out, and not talkative is 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, carry out ozone diffusion while carry out sample edge to leach liquor, acid concentration is set to 1N and ozone is set to 190 minutes diffusion time, except these 3, with above-mentioned 2) under sulfuric acid, carry out ozone diffusion under identical condition, implement and make manganese form oxide compound and solidified experiment.

The sampling of leach liquor is before ozone diffusion and carry out in ozone DIFFUSION TREATMENT.In addition, the sampling in ozone DIFFUSION TREATMENT with carry out repeatedly diffusion time through ozone simultaneously.When sampling leach liquor, confirming that leach liquor fully stirs and becomes uniform state, sampling 50cm respectively ³.Filtered by the leach liquor of the membrane filter of 0.22 μm to sampling, isolate Mn oxide, observe the color of filtrate (solvent portions).

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

(solid) is not precipitated in the leach liquor of sampling before ozone diffusion.In addition, solid manganese attaches on the reaction vessel with film like as mentioned above, quantitative generation error, therefore, in the filtrate of sample before ozone DIFFUSION TREATMENT in manganese concentration and ozone DIFFUSION TREATMENT the filtrate side of sample manganese concentration based on calculate manganese recovery ratio (quality base).It should be noted that, manganese concentration in filtrate is undertaken quantitatively by ICP emission spectrometry method.

Experimental result is shown in Fig. 6.

Fig. 6 represents the change along with the process of ozone diffusion time of the color of filtrate and manganese recovery ratio.As shown in Figure 6, can to think after ozonization soon, the organism in medium component leach liquor that results from consumes ozone, does not produce the generation of Mn oxide.After about 100 minutes, start to generate Mn oxide, meanwhile, leach liquor promptly becomes black.But in this moment, if carry out filtration to remove Mn oxide, then the color eliminating the filtrate (solvent portions) of Mn oxide becomes and is considered to result from the light yellow of medium component.In addition, if start to generate Mn oxide, then along with the process of ozone diffusion time, simultaneously manganese recovery ratio rises rapidly at short notice, ozone be diffusion time reach near 150 minutes more than 99% manganese recovery ratio.

But ozone spread if keep original state to continue ozone, then manganese recovery ratio reduction diffusion time after 150 minutes.Now, the color of filtrate become the color of the superoxide as manganese red ~ red-violet colour.Can draw following conclusion by these results: in ozone diffusion time after 150 minutes, generate the superoxide of manganese, manganese peroxidase becomes ion and is again dissolved in reaction solution, and 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 shown in, in acid ozone DIFFUSION TREATMENT, obtain high manganese recovery ratio in there is best ozone diffusion time.But best ozone is easily subject to the impact of the composition, reactor shape, bubble footpath, stirring velocity etc. of reaction soln diffusion time.Therefore, it is extremely difficult for predetermining best ozone diffusion time based on the Fe content of the kind of iron-reducing bacteria, treated object, other acid ozone DIFFUSION TREATMENT condition (ozone diffusing capacity, acid concentration etc.).

Shown in table 8 is the result (batch No.1A ~ 4A) of carrying out 4 following experiments and obtaining, described experiment is as follows: ozone is set to 150 minutes diffusion time, namely be set to 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, obtain the ratio of the absorbancy of solution when starting with reaction.

[table 8]

As shown in table 8, though ozone diffusion time and other condition identical, manganese recovery ratio also can be uneven, obtain more than the color being only filtrate of 99% rate of recovery be 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 spread with ozone before the ratio of absorbancy of (0 minute), then can confirm, owing to generating manganese peroxide ion, solution is colored, absorbancy increases according to its growing amount.Because generation manganese peroxide ion is trace time " batch No.1A ", therefore, maintain the higher rate of recovery, but in " batch No.4A ", the generation of manganese peroxide ion is superfluous, thinks that loss increases.As known from the above, for the management of ozone diffusion time, it is difficult for manganese recovery ratio being stablized and reaches maximum.

On the other hand, shown in table 9 is the result (batch No.1B ~ 4B) of carrying out 4 following experiments and obtaining, described experiment is as follows: judge that the color of filtrate becomes the ruddy moment as " 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, become the ruddy moment in the color of filtrate terminate acid ozone DIFFUSION TREATMENT from light yellow.

[table 9]

As shown in table 9, carry out observation by the color of the filtrate to leach liquor and determine manganese oxidizing reaction terminal (ozone diffusion time), can continue to obtain the rate of recovery more than 99%.In addition, now, from the measurement result of absorbancy, in either case, all the generation of manganese peroxide ion is suppressed lower, can not produce and excessively or insufficiently react, thus the rate of recovery reaches maximum.

As above describe, due to the impact adopting the manganese oxidizing reaction of ozone to be subject to the composition, reactor shape, bubble footpath, stirring velocity etc. of reaction soln, therefore, identical manganese recovery ratio may not be obtained in the identical reaction times (ozone diffusion time).Particularly, under use make use of the situation of the manganese leach liquor of microorganism etc., think that the composition of leach liquor produces larger change because of microbic activity and bacterium number etc., therefore, comparatively difficult to the management in reaction times, unrealistic.On the other hand, even if such as when the composition of leach liquor produces larger change because of microbic activity and bacterium number etc., observing 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, the treated object containing iron-reducing bacteria, treatment solution, manganese shown below is used to carry out

The leaching of the manganese utilizing iron-reducing bacteria to carry out.

< iron-reducing bacteria >

ShewanellaalgaeNBRC103173 strain

(NITE Biological Resource Center)

< treatment solution >

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

Treatment solution B: with the addition of above-mentioned iron-reducing bacteria and the treatment solution obtained 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

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

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

< treated object >

The metallic dust (Mn:69 quality %, Fe:3 quality %) produced by the refining procedure of iron work

[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

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

The temperature for the treatment of solution: 25 DEG C

The pH:7 for the treatment of solution

Treatment time: 24 hours

Atmosphere: anaerobic condition

After above-mentioned leaching process terminates, with the membrane filter of 0.45 μm, obtained manganese leach liquor is filtered.The concentration of manganese contained in the sample (filtrate) after filtration is undertaken quantitatively by high-frequency inductive coupling plasma body emission spectrometry (ICP emission spectrometry).Quantitative result is shown in table 11.

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

After process, filter with the membrane filter of 0.22 μm, solid is weighed after dry 3 days at 50 DEG C.

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

[table 11]

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

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

In addition, the content comprising the manganese in the solid of the manganese reclaimed by ozone DIFFUSION TREATMENT, carbon and phosphorus is manganese when employing treatment solution A: 45 quality %, carbon: 0.14 quality %, phosphorus: 0.8 quality %, on the other hand, when employing 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 relative to manganese containing ratio.

Claims

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

Insoluble operation, after this solid-liquid separation process, the pH of the parting liquid containing mn ion and 3 valency iron ions and redox potential are adjusted to pH and the redox potential in the region that solidification also precipitates with manganese formation oxide compound in redox potential-pH figure, thus make it insoluble mn ion contained in described parting liquid oxidation; And

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

Recycling containing the treatment solution of parting liquid after the recovery of ferric ion as described leaching operation of manganese composition will have been reclaimed from described parting liquid.

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

Described insoluble operation is the parting liquid effect after making ozone and described solid-liquid separation process in acid condition, the operation making it insoluble mn ion oxidation thus.

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

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

Described treated object 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.

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

7. manganese recovery method according to claim 3, wherein,

8. manganese recovery method according to claim 4, wherein,

9. the manganese recovery method according to any one of claim 1 ~ 8, wherein,

In described insoluble operation, take out the liquid in insoluble process termly or continuously, observe the colour-change of the solvent portions of the liquid taken out, differentiate the oxidizing reaction terminal of mn ion thus.

10. the manganese recovery method according to any one of claim 1 ~ 8, wherein,

Treatment solution in described leaching operation is the treatment solution limiting carbon concentration and phosphorus concentration.

11. manganese recovery methods according to claim 9, wherein,

12. manganese recovery methods according to claim 10, wherein,

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

13. manganese recovery methods according to claim 11, wherein,