Indian Patents. 239996:A PROCESS FOR MICROBIAL LEACHING OF MANGANESE FROM MANGANESE ORE

Title of Invention	A PROCESS FOR MICROBIAL LEACHING OF MANGANESE FROM MANGANESE ORE
Abstract	A process for microbial leaching of manganese from manganese.The solubilisation process takes place at room temperature,atmospheric pressure and lixiviant containing mineral salt medium along with Penicillium citrinum cultures.Upto 65% of manganese extraction from manganese ore could be achieved with the process in 30 days.

Full Text	The present investigation relates to a novel process for the microbial extraction of manganese from manganese ore. Background of the Invention The invention, in particular, relates to a successful microbial process for solubilisation of manganese from manganese ore using Penicillium citrinum. The total recoverable resources of manganese ore in India is 167 million tones. Karnataka has the main share at 36.57% which is followed by Orissa at 23.14%.In India, significant lean deposits with manganese concentrations less than 35% exist, which are ignored because extraction methods applied to rich manganese ore cannot be economically used with them. The manganese ore as mined may not be suitable for utilisation in the manufacture of ferromanganese alloys and therefore, it requires processing, to improve its quality by reducing the deliterious constituents with a simultaneous increase in the manganese content. Recovery of metals from low-grade ores using the existing technology is prohibitively expensive due to high energy and capital costs. Another major problem in many parts of the world is the rising cost of environmental protection.In such circumstances, bioleaching comes into the picture.lt is regarded as one of the most promising and revolutionary solutions to these problems. Oxidation and reduction of manganese have been recognized as microbially catalyzed reactions since the beginning of the century (l).Some mycelial fungi have been found to reduce manganese oxides under laboratory conditions. In the indirect mechanism, reductive process is associated with the formation of reductive compounds, resulting from their metabolism (2,3). Non-enzymatic reduction of manganese oxides by fungi is best explained in terms of production of metabolic products by them that act as reductants. The dissolution of Mn (IV) by organic microbial metabolites such as formate, oxalate, pyruvate and salicylate has been described (Stone, A. T. and Morgan ,JJ. 1984. Environ. Sic. Technol. 18:617-620; 5.Stone, A .T. 1987.Geochim .Cosmochim. Acta 514:919-925). The above mentioned property of non-enzymatic reduction of manganese oxides by fungi has been utilized for extraction of manganese from manganese ore. The main objective of the present invention is microbial leaching of manganese ore using Penicillium citrinum MTCC 3303 for extraction of manganese under mild fermentation condityion. Another object of the invention is to produce manganese by eco friendly process. Novelty of the process lies in the use of Penicillium citrinum and the specific medium composition used for this process. Accordingly, the present invention provides a process for microbial leaching of manganese from manganese ore which comprises (a) preparing a culture medium and autoclaving the said medium; (b) inoculation of fungal culture Penicillium citrinum with 10%v/v of culture medium and addition of manganese ore 2-3% w/v; (c) incubating the inoculated culture as in step (b) for a period of 30-35 days on a rotatry shaker at a temperature ranging 27-32 °C ; (d) recovering the manganese from the cultured broth by known methods. In an embodiment of the present invention a microbial strain Penicillium citrinum deposited at MTCC chandigarh bearing No.3303 and having been isolated from top soil of Joda manganese mines. In another embodiment of the present invention a microbial strain Penicillium citrinum at MTCC chandigarh bearing No.3303 as claimed in claim 1-2 and said microbial strain comprising growth characteristic of growing rapidly on agar in 10-12 days at 25 C-30°C and the colonies typically furrowed in radial pattern, velvety with a white margin ranging about 0.2 to 2 mm in width.and with characteristics penicillus comprising of 3-5 divergent and usually vesiculate metulae and the said metulae bearing long well defined columns of conidia and conidia en masse being blue grey in colour and conidiophores being borne from subsurface or surface hyphae, stipes being 100 - 300 x 2.2 - 3.0 urn, smooth walled, terminating in well-defined verticles ranging 3-5 divergent metulae and the conidia spheroidal to subspheroidal borne in long well defined columns being one per metula and arranged in a characteristic whorl on each conidiophore. In yet another embodiment of the present invention the culture medium comprising: Ammonium nitrate 3.0 g/1. Potassium dihydrogen phosphate 1.0g/l, Magnesium sulphate 0.5g/l and Sucrose l00.0g/l with pH adjusted to 6.5 with dilute sodium hydroxide In an embodiment of the present invention the selected manganese ore used as substrate has particle size in the range of 45-2812 micron In an embodiment of the present invention the composition of manganese ore comprises of about 29% manganese and about 35%w/w iron. In still another embodiment of the present invention the concentration of manganese ore used ranges from 2-3% w/v In yet another embodiment of the present invention the yield of manganese is in the range of 33-65%w/w of the ore used Detailed Description The major steps in the process are : i) Isolation and identification of manganese solubilising microorganisms from top soil of manganese mine area; ii) Inoculation of Penicillium citrinum in the lixiviant; ii) Leaching of manganese ore; The process of this invention is illustrated by examples which should not be construed to limit the scope of this invention. Example-1 90 ml of mineral salt medium was taken in 250ml Erlenmeyer flask. 10ml of fully grown Penicillium citrinum culture was added. 2 gm of manganese ore of size 500 microns was also added to it. The pH was adjusted to 6.5 by dilute NaOH dropwise. The flasks were incubated at 32°C on a rotary shaker(140 rpm).At the end of 30 days,the flask's contents were filtered. After completion of bioleaching, the flasks containing manganese ore, microorganism and the media were sterilised. The leached product underwent solid-liquid separation. The leach liquor contained 0.8gpl manganese and 0.006 gpl of iron. The solid residue which had acid soluble manganese after solid-liquid separation was leached with 5M H2SO4. The leach liquor obtained after acid leaching contained 2gpl manganese and 0.5 gpl iron. The manganese recovered after bacterial leaching and acid leach were mixed and the concentration of Mn and Iron were 1.4 gpl and 0.25 gpl respectively. The precipitation of iron from the lean leach liquor was done using 10% lime slurry. The pH was adjusted to 6.0 by adding lime slurry. After precipitation of iron as iron hydroxides, the leach liquor contained only 0.0020 gpl of iron. Corresponding precipitation of manganese was taken as very little, hence leach liquor contained 1.4gpl manganese. The leach liquor containing manganese as sulphate can be crystallised to get manganous sulphate (MnSO4.7H2O) by standard technique which has several use. After completion of bioleaching, the flasks containing manganese ore, microorganism and the media were sterilised. The leached product underwent solid-liquid separation. The leach liquor contained 0.8gpl manganese and 0.006 gpl of iron. The solid residue which had acid soluble manganese after solid-liquid separation was leached with 5M H2SO4. The leach liquor obtained after acid leaching contained 2gpl manganese and 0.5 gpl iron. The manganese recovered after bacterial leaching and acid leach were mixed and the concentration of Mn and Iron were 1.4 gpl and 0.25 gpl respectively. The precipitation of iron from the lean leach liquor was done using 10% lime slurry. The pH was adjusted to 6.0 by adding lime slurry. After precipitation of iron as iron hydroxides, the leach liquor contained only 0.0020 gpl of iron. Corresponding precipitation of manganese was taken as very little, hence leach liquor contained 1.4gpl manganese. The leach liquor containing manganese as sulphate can be crystallised to get manganous sulphate (MnSO4.7H2O) by standard technique which has several use. .The overall manganese extraction was taken to be the sum of acid desorbed and soluble manganese at the termination of the experiment. The manganese and iron extraction came out to be 33% and 7%respectively. Example-2 90 ml of mineral salt medium was taken in 250ml Erlenmeyer flask. 10ml of fully grown Penicillium citrinum culture was added.2 gm of manganese ore of size 45 microns was also added to it. The pH was adjusted to 6.5 by dilute NaOH dropwise. The flasks were incubated at 32°C on a rotary shaker(140 rpm).At the end of 30 days,the flask's contents were filtered.The biomass and the ore which remained on the filter paper were thoroughly washed with distilled water and then with dilute sulphuric acid. The manganese extraction was 65% and the iron extraction was 12% at the end of 30 days. Advantages The main advantages of the present invention are : (a) The process is carried out under mild conditions without the addition of toxic chemicals. (b) It holds the promise of lowering the fixed capital costs as well as offers the opportunity to reduce environmental pollution. (c) The process neither requires sophisticated instrumentation nor skilled manpower. (d) The process is economical even at moderate scale. (e) The end product, manganous sulphate can be utilized for production of manganese dioxide which has several use Apart from above there is a global demand of manganese for its use in manufacturing of steel and other ferro manganese alloys. (f) The process utilizes naturally occurring soil microorganisms which are thus not hazardous to human beings We claim: 1. A process for microbial leaching of manganese from manganese ore which comprises (a) preparing a culture medium and autoclaving the said medium; (b) inoculation of fungal culture Penicillium citrinum with 10%v/v of culture medium and addition of manganese ore 2-3% w/v; (c) incubating the inoculated culture as in step (b) for a period of 30-35 days on a rotatry shaker at a temperature ranging 27-32 °C ; (d) recovering the manganese from the cultured broth by known methods. 2. A process for microbial leaching of manganese as claimed in claim 1, wherein the culture medium comprises ammonium nitrate 3.0g/l, potassium dihydrogen phosphate 1.0 g/1, magnesium sulphate 0.5 g/1 and sucrose 100.0g/l with pH adjusted to 6.5 with dilute sodium hydroxide. 3. A process for microbial leaching of manganese from manganese ore substantially as herein described with references to examples.

Full Text

The present investigation relates to a novel process for the microbial extraction of manganese from manganese ore.
Background of the Invention
The invention, in particular, relates to a successful microbial process for solubilisation of manganese from manganese ore using Penicillium citrinum.
The total recoverable resources of manganese ore in India is 167 million tones. Karnataka has the main share at 36.57% which is followed by Orissa at 23.14%.In India, significant lean deposits with manganese concentrations less than 35% exist, which are ignored because extraction methods applied to rich manganese ore cannot be economically used with them. The manganese ore as mined may not be suitable for utilisation in the manufacture of ferromanganese alloys and therefore, it requires processing, to improve its quality by reducing the deliterious constituents with a simultaneous increase in the manganese content. Recovery of metals from low-grade ores using the existing technology is prohibitively expensive due to high energy and capital costs. Another major problem in many parts of the world is the rising cost of environmental protection.In such circumstances, bioleaching comes into the picture.lt is regarded as one of the most promising and revolutionary solutions to these problems. Oxidation and reduction of manganese have been recognized as microbially catalyzed reactions since the beginning of the century (l).Some mycelial fungi have been found to reduce manganese oxides under laboratory conditions. In the indirect mechanism, reductive process is associated with the formation of reductive compounds, resulting from their metabolism (2,3). Non-enzymatic reduction of manganese oxides by fungi is best explained in terms of production of metabolic products by them that act as reductants. The dissolution of Mn (IV) by organic microbial metabolites such as formate, oxalate, pyruvate and salicylate

has been described (Stone, A. T. and Morgan ,JJ. 1984. Environ. Sic. Technol. 18:617-620; 5.Stone, A .T. 1987.Geochim .Cosmochim. Acta 514:919-925).
The above mentioned property of non-enzymatic reduction of manganese oxides by fungi has been utilized for extraction of manganese from manganese ore.
The main objective of the present invention is microbial leaching of
manganese ore using Penicillium citrinum MTCC 3303 for extraction of manganese under mild fermentation condityion.
Another object of the invention is to produce manganese by eco friendly process.
Novelty of the process lies in the use of Penicillium citrinum and the specific medium composition used for this process.
Accordingly, the present invention provides a process for microbial leaching of manganese from manganese ore which comprises
(a) preparing a culture medium and autoclaving the said medium;
(b) inoculation of fungal culture Penicillium citrinum with 10%v/v of culture medium and addition of manganese ore 2-3% w/v;
(c) incubating the inoculated culture as in step (b) for a period of 30-35 days on a rotatry shaker at a temperature ranging 27-32 °C ;
(d) recovering the manganese from the cultured broth by known
methods.
In an embodiment of the present invention a microbial strain Penicillium citrinum deposited at MTCC chandigarh bearing No.3303 and having been isolated from top soil of Joda manganese mines.
In another embodiment of the present invention a microbial strain Penicillium citrinum at MTCC chandigarh bearing No.3303 as claimed in claim 1-2 and said microbial strain comprising growth characteristic of growing rapidly on agar in 10-12 days at 25 C-30°C and the colonies typically furrowed in radial

pattern, velvety with a white margin ranging about 0.2 to 2 mm in width.and with characteristics penicillus comprising of 3-5 divergent and usually vesiculate metulae and the said metulae bearing long well defined columns of conidia and conidia en masse being blue grey in colour and conidiophores being borne from subsurface or surface hyphae, stipes being 100 - 300 x 2.2 - 3.0 urn, smooth walled, terminating in well-defined verticles ranging 3-5 divergent metulae and the conidia spheroidal to subspheroidal borne in long well defined columns being one per metula and arranged in a characteristic whorl on each conidiophore.
In yet another embodiment of the present invention the culture medium comprising: Ammonium nitrate 3.0 g/1. Potassium dihydrogen phosphate 1.0g/l, Magnesium sulphate 0.5g/l and Sucrose l00.0g/l with pH adjusted to 6.5 with dilute sodium hydroxide
In an embodiment of the present invention the selected manganese ore used as substrate has particle size in the range of 45-2812 micron
In an embodiment of the present invention the composition of manganese ore comprises of about 29% manganese and about 35%w/w iron.
In still another embodiment of the present invention the concentration of manganese ore used ranges from 2-3% w/v
In yet another embodiment of the present invention the yield of manganese is in the range of 33-65%w/w of the ore used
Detailed Description
The major steps in the process are : i) Isolation and identification of manganese solubilising microorganisms from top soil of manganese mine area;
ii) Inoculation of Penicillium citrinum in the lixiviant; ii) Leaching of manganese ore;
The process of this invention is illustrated by examples which should not be construed to limit the scope of this invention.
Example-1
90 ml of mineral salt medium was taken in 250ml Erlenmeyer flask. 10ml of fully grown Penicillium citrinum culture was added. 2 gm of manganese ore of size 500 microns was also added to it. The pH was adjusted to 6.5 by dilute NaOH dropwise. The flasks were incubated at 32°C on a rotary shaker(140 rpm).At the end of 30 days,the flask's contents were filtered. After completion of bioleaching, the flasks containing manganese ore, microorganism and the media were sterilised. The leached product underwent solid-liquid separation. The leach liquor contained 0.8gpl manganese and 0.006 gpl of iron. The solid residue which had acid soluble manganese after solid-liquid separation was leached with 5M H2SO4. The leach liquor obtained after acid leaching contained 2gpl manganese and 0.5 gpl iron. The manganese recovered after bacterial leaching and acid leach were mixed and the concentration of Mn and Iron were 1.4 gpl and 0.25 gpl respectively. The precipitation of iron from the lean leach liquor was done using 10% lime slurry. The pH was adjusted to 6.0 by adding lime slurry. After precipitation of iron as iron hydroxides, the leach liquor contained only 0.0020 gpl of iron. Corresponding precipitation of manganese was taken as very little, hence leach liquor contained 1.4gpl manganese. The leach liquor containing manganese as sulphate can be crystallised to get manganous sulphate (MnSO4.7H2O) by standard technique which has several use. After completion of bioleaching, the flasks containing manganese ore, microorganism and the media were sterilised. The leached product underwent solid-liquid separation. The leach liquor contained 0.8gpl manganese and 0.006 gpl of iron. The solid residue which had acid soluble manganese after solid-liquid separation was leached with 5M H2SO4. The leach liquor obtained after acid leaching contained 2gpl manganese and 0.5 gpl iron. The manganese recovered after bacterial leaching and acid leach were mixed and the concentration of Mn and Iron were 1.4 gpl and 0.25 gpl respectively. The precipitation of iron from the lean leach liquor was done using 10% lime slurry. The pH was adjusted to 6.0 by adding lime slurry. After precipitation of iron as iron hydroxides, the leach liquor contained only 0.0020 gpl of iron. Corresponding precipitation of manganese was taken as very little, hence leach liquor contained 1.4gpl manganese. The leach liquor containing manganese as sulphate can be crystallised to get
manganous sulphate (MnSO4.7H2O) by standard technique which has several use. .The overall manganese extraction was taken to be the sum of acid desorbed and soluble manganese at the termination of the experiment.
The manganese and iron extraction came out to be 33% and 7%respectively.
Example-2
90 ml of mineral salt medium was taken in 250ml Erlenmeyer flask. 10ml of fully grown Penicillium citrinum culture was added.2 gm of manganese ore of size 45 microns was also added to it. The pH was adjusted to 6.5 by dilute NaOH dropwise. The flasks were incubated at 32°C on a rotary shaker(140 rpm).At the end of 30 days,the flask's contents were filtered.The biomass and the ore which remained on the filter paper were thoroughly washed with distilled water and then with dilute sulphuric acid.
The manganese extraction was 65% and the iron extraction was 12% at the end of 30 days.
Advantages
The main advantages of the present invention are :
(a) The process is carried out under mild conditions without the addition of toxic chemicals.
(b) It holds the promise of lowering the fixed capital costs as well as offers the opportunity to reduce environmental pollution.
(c) The process neither requires sophisticated instrumentation nor skilled manpower.
(d) The process is economical even at moderate scale.
(e) The end product, manganous sulphate can be utilized for production of manganese dioxide which has several use Apart from above there is a global demand of manganese for its use in manufacturing of steel and other ferro manganese alloys.
(f) The process utilizes naturally occurring soil microorganisms which are thus not hazardous to human beings

We claim:
1. A process for microbial leaching of manganese from manganese ore
which comprises
(a) preparing a culture medium and autoclaving the said medium;
(b) inoculation of fungal culture Penicillium citrinum with 10%v/v of culture medium and addition of manganese ore 2-3% w/v;
(c) incubating the inoculated culture as in step (b) for a period of 30-35 days on a rotatry shaker at a temperature ranging 27-32 °C ;
(d) recovering the manganese from the cultured broth by known
methods.
2. A process for microbial leaching of manganese as claimed in claim 1, wherein the culture medium comprises ammonium nitrate 3.0g/l, potassium dihydrogen phosphate 1.0 g/1, magnesium sulphate 0.5 g/1 and sucrose 100.0g/l with pH adjusted to 6.5 with dilute sodium hydroxide.
3. A process for microbial leaching of manganese from manganese ore substantially as herein described with references to examples.

Documents:

529-DEL-2004-Abstract-(09-03-2010).pdf

529-del-2004-abstract.pdf

529-DEL-2004-Claims-(09-03-2010).pdf

529-del-2004-claims.pdf

529-DEL-2004-Correspondence-Others-(09-03-2010).pdf

529-del-2004-correspondence-others.pdf

529-del-2004-correspondence-po.pdf

529-DEL-2004-Description (Complete)-(09-03-2010).pdf

529-del-2004-description (complete).pdf

529-DEL-2004-Form-1-(09-03-2010).pdf

529-del-2004-form-1.pdf

529-del-2004-form-18.pdf

529-DEL-2004-Form-2-(09-03-2010).pdf

529-del-2004-form-2.pdf

529-DEL-2004-Form-3-(09-03-2010).pdf

529-del-2004-form-3.pdf

529-del-2004-form-5.pdf

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Patent Number

239996

Indian Patent Application Number

529/DEL/2004

PG Journal Number

30/04/2010

Publication Date

30-Apr-2010

Grant Date

21-Apr-2010

Date of Filing

19-Mar-2004

Name of Patentee

See attached documents

Applicant Address

See attached documents

Inventors:

#	Inventor's Name	Inventor's Address
1	See attached documents	See attached documents

PCT International Classification Number

C 22 B 47 /00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA