CN104480314B - Method for recycling waste residue in manganese industry production - Google Patents
Method for recycling waste residue in manganese industry production Download PDFInfo
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- CN104480314B CN104480314B CN201410787589.4A CN201410787589A CN104480314B CN 104480314 B CN104480314 B CN 104480314B CN 201410787589 A CN201410787589 A CN 201410787589A CN 104480314 B CN104480314 B CN 104480314B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a method for recycling waste residue in manganese industry production. The method comprises the specific following steps: (1) pre-processing filter residue; (2) adding acid and leaching; (3) carrying out filtering and solid-liquid separation on ore slurry; (4) recovering hematite powder; (5) recovering manganese carbonate concentrate; and (6) preparing a nitrogen-phosphorus compound fertilizer base material. By the method, hematite powder, manganese carbonate concentrate and the nitrogen-phosphorus compound fertilizer base material can be recovered from leached press-filtered residue, the process is simple and is easy to achieve industrialization and meanwhile, the content of the heavy metal ingredients is in completely in conformity with national associated standards, treated wastewater and waste residue are free of harmful ingredients such as heavy metals, the environmental pressure is alleviated and the method has great promotional values.
Description
Technical field
The invention belongs to abandoned mine slag for comprehensive utilizes technology, reclaim in particular with filter-press residues are leached in electrolytic manganese metal production
The method for making various chemical products.
Background technology
, used as one of important strategic resource of national economy, China is the Eleventh Five-Year Plan period also by manganese as country's war for manganese
Omit resource.At present, manganese is mainly obtained by electrolysis and reducing process, and be electrolysed legal system manganese account for pure manganese produce the 95% of total amount with
On, it is raw material with manganese spar and pyrolusite that the manufacturing enterprise of electrolytic manganese metal is all, Jing sulfuric acid leachings → oxidizer oxidation two
Valency iron → ammonification water neutralizing hydrolysis is except iron → leaching press filtration (filter-press residues) → filtrate → plus the heavy metals of SDD (Sodium Dimethyldithiocarbamate)
(Co, Ni, Cu) → secondary press filtration → filtrate staticly settles → suction filtration clear liquid → electrolysis → electrolytic manganese metal.Its process produces a large amount of
Turnover filter-press residues, slag rate are directly transported to slag storehouse up to one ton of electrolytic manganese metal is often produced with regard to the leaching filter-press residues of output 6-8 ton
Lose and put.And in this slag, also contain many useful elements, such as：The middle leaching filter-press residues for believing big Meng great Xin Meng industry Co., Ltd are just
Have：Manganese sulfate 12%, silica 30-40%, calcium sulfate 5-10%, magnesium sulfate 3-4%, aluminum oxide 13%, iron hydroxide
20%th, ammonium sulfate 2-3%, so not only lost valuable mineral resources, and occupies substantial amounts of land resource, to ring
Border is polluted and geological disaster has very big hidden danger.
Notification number discloses a kind of " technique of electrolytic manganese residues comprehensive utilization " its technique for the patent document of CN10306425B
It is to clean leached mud and be concentrated by evaporation to reclaim soluble manganese and ammonium sulfate, remaining waste residue brickmaking with water circulation.Which has the disadvantage only to return
Part soluble manganese and ammonium sulfate is received, but has been failed to be reclaimed and do not leach and water-fast valuable mineral, and power consumption consumption
Water is big, and cost recovery is too high.
Process of the inventor to electrolytic manganese waste residue is reclaimed and is had made intensive studies, and has applied for Patents：" electrolytic metal
Leached mud comprehensive reutilization method in manganese, manganese dioxide production ", Patent No. ZL201210179516.8, the method are adopted
Heavy, floating, magnetic separation and chemical-biological the technique such as leach and carry out comprehensive reutilization, although reclaim more comprehensively valuable metal mineral and
Composite fertilizer's base-material is prepared, but process route is oversize in implementation process, the auxiliary material for using and plant equipment are too many, and floor space is too
Greatly, under conditions of continuous summing up experience and improving production technology, the more advanced practical, method of simple possible has been invented.
The content of the invention
It is an object of the invention to provide a kind of manganese industry produces the method that waste residue is recycled, the method can reclaim iron oxide red ore deposit
Powder, carbonic acid manganic concerntrate, prepare prodan and compound nitrogen phosphate fertilizer base-material, with solve current waste residue recovery processing technique route length,
Using auxiliary material and plant equipment be more, place of production area big, high problem is lost.
For achieving the above object, technology path of the invention is realized in：
A kind of method that manganese industry production waste residue is recycled, concrete technology include following part：(1) filter residue pretreatment；(2)
Acid adding is leached；(3) slurry filtration and separation of solid and liquid；(4) iron oxide red breeze is reclaimed；(5) carbonic acid manganic concerntrate is reclaimed；(6) nitrogen phosphorus is combined
It is prepared by fertile base-material.
Filter residue pretreatment is that filter residue first to add water crush after mixing as ore pulp, then again by spiral classifier classification
Afterwards, make not cross the ore particle Jing wet ball mills fine grinding of 100 mesh sieves until crossing 100 mesh sieves.Because electrolytic manganese, manganese dioxide filter residue are to contain
Solid block of the liquid measure for 28-30%, must have under water state and to smash into ore pulp in disintegrating machine；The size distribution of ore pulp is general
100 mesh sieves are crossed for 84%, 16% does not cross 100 mesh sieves, that is, the screenings for having 84% ore particle to be 100 mesh sieves has 16% ore particle to be 100
The oversize of mesh sieve.Ore particle on 16% sieve is made to reach into wet ball mill fine grinding so ore pulp carries out classification through spiral classifier
To the granularity requirements for leaching.
It is to add the concentrated sulfuric acid in ore pulp that the acid adding is leached, and control system pH≤1.5 make Fe3+、Mn2+With ionic condition
Leach in ore pulp；
The slurry filtration and separation of solid and liquid are to squeeze into filter press with wear-resisting resistance to acid attack Pulp pump to carry out separation of solid and liquid, gained
Filter cake does peroxophosphoric acid calcareous fertilisers use, and gained filtrate is into the process of lower step operation；
The iron oxide red breeze is reclaimed once to be neutralized in step (3) is obtained filtrate, adds ammonium alkali to adjust pH to 4-5, makes
Fe(OH)3Precipitation, Jing filter press press filtrations, gained Washing of Filter Cake dry to obtain iron oxide red breeze；
It is the secondary neutralization in step (4) is obtained filtrate that the carbonic acid manganic concerntrate is reclaimed, and adds ammonium alkali and adjusts pH7.2-
8, make MnSO4Precipitation, diaphragm filter press press filtration separation of solid and liquid, gained Washing of Filter Cake dry to obtain carbonic acid manganic concerntrate, gained filter
It is 7 that the liquid concentrated sulfuric acid is neutralized to pH, sends cycling use of water pond back to；
Prepared by the compound nitrogen phosphate fertilizer base-material concretely comprises the following steps：
1. obtained filter cake recirculated water in step (3) is ground into into slurry in pulverizer, is put into slurry bucket；
2. add P2O5Content is >=26% fluorine-containing low ground phosphate rock stirring is made into slurry, into mixing reactor, standby
With；
3. add concentrated sulfuric acid hybrid reaction 3-5min of weight concentration more than 90%, after the completion of flow into the reaction of belt formation chamber
30min；
4. aerobic fermentation tank curing 7-15d is sent into, dries pulverizing is obtained final product；
The ammonium alkali is the one kind in ammonium hydrogen carbonate, ammonium carbonate or ammoniacal liquor.
When the silicate fluoride solution content that the Jing acid fog absorption towers are formed is less than 8%, into circulating water pool.
The present invention is had an advantage in that compared with prior art：
First, ferrimanganic resource can more fully and effectively be reclaimed.
(1) grinding is cleaned by being diluted with water again smashing classification, which decrease CaSO4Degree of supersaturation, also destroy
It is wrapped in the CaSO on ore particle surface4Wrap film makes ore particle easily leach；
(2) the press filtration separation of solid and liquid under low pH value, it is to avoid metal ion follows filter residue to walk with colloidal, lost
Iron, manganese Metal, increased the content of beary metal of filter residue.
2nd, using by the volatile fertilizer ammonium alkali (NH being easy to run off of thermally labile4HCO3、(NH4)2CO3、NH3·H2O) sink
Iron, manganese Metal have not only been reclaimed in shallow lake agent, and make to be easy to run off ammonium alkali fertilizer to become stable (NH4)2SO4Nitrogen manure raw material.
3rd, substantial amounts of (NH in the calcium dihydrogen phosphate for being generated using ground phosphate rock and strong sulfuric acid response and the filter residue aqueous solution4)2SO4
Reaction generates MAP and prepares NP composite fertilizers base-material.
4th, production electrolytic manganese metal and phosphorization product are engaged in using manganese resource and phosphate rock resource and realize arranging without waste residue
The target put.
Description of the drawings
Fig. 1 is the process chart that manganese industry produces the method that waste residue is recycled.
See in figure, the concrete technology of the present invention is as follows：Manganese filter-press residues add water first and are crushed and ball milling, then enriching
Sulfuric acid leaching；Ore pulp press filtration, filter cake enter reactor, add the concentrated sulfuric acid and fluorine-containing low ground phosphate rock, solid curing to make nitrogen phosphorus
Composite fertilizer；Filtrate once neutralizes press filtration again, and Washing of Filter Cake drying obtains iron oxide red；The secondary neutralization of filtrate, press filtration, washing and drying are obtained
Carbonic acid manganic concerntrate.
Specific embodiment
Embodiment one
1st, leaching filter-press residues 1000g and 8L clear water is weighed, disintegrating machine smashing is put into and is made into ore pulp, and cross 100 eye mesh screens, sieve
Lower thing is entered crosses 100 eye mesh screens and with addition after chemical combination agitator, oversize add 2L clear water together to grind into minigrinder
Chemical combination agitator, starts mixer, is stirred with 65 turns/min mixing speeds.
2nd, measure 98%H2SO4500ml, adds while stirring and mixes in bucket, continues stirring 4h or so, measures pH value
For 1.5, terminate stirring.
3rd, filter separation of solid and liquid, filter residue puts well and continue to employ, and filtrate is put into neutralizing hydrolysis agitator, starts mixer, with 65 turns/
Min mixing speeds are stirred.
4th, NH is slowly added to while stirring4HCO3Powder, once neutralizes, test solution pH value, when PH is 4, stops adding
NH4HCO3, continue stirring and produce to bubble-free, terminate stirring.
5th, separation of solid and liquid is filtered, filtrate is put into neutralization precipitation agitator, and filter residue clear water is washed three times, and washings are together put
Enter neutralization precipitation agitator, filter residue drying 168gFe content at 107 DEG C is 35% iron oxide red breeze after washing.As a result see
Survey report 1.
6th, start neutralization precipitation agitator mixer and be stirred with 65 turns/min rotating speeds, be slowly added to while stirring
NH4HCO3Powder, secondary neutralization is while test solution pH value, when PH is 7.2, stops adding NH4HCO3Powder, continues stirring to nothing
Bubble is produced, and terminates stirring.
7th, separation of solid and liquid is filtered, filtrate is put in neutralization precipitation agitator, and filter residue clear water is washed three times, and cleaning solution is in the lump
Neutralization agitator is put into, filter residue drying 125gMn content at 107 DEG C is 31% MnCO3Concentrate, is shown in examining report 2.
8th, start neutralization agitator mixer and be stirred with the mixing speed of 65 turns/min, add 98% while stirring
H2SO4, while testing pH value, when PH is 7.2, stop adding 98%H2SO4, continue to terminate stirring when stirring to bubble-free is produced
Mix, and solution is put in circulation bucket in case lower circulation is used.
9th, measure in " Section 8 " filter residue in circulation bucket in solution 2L and " Section 3 " and be put into disintegrating machine and smash into ore deposit
Slurry, pours in " Section 9 " in hybrid reaction bucket, starts agitator, and be stirred by 65 turns/min of rotating speed, clear water is noted
Enter to absorb in bucket at 2/3.
10th, weigh containing P2O5For 30%, SiO2For 3.42% ground phosphate rock 1000g, " Section 10 " hybrid reaction bucket is added
In, after stirring 3min, then measure 98%H2SO4Solution 500ml is slowly added into hybrid reaction bucket, stops stirring, mixed after 15min
In closing reaction container, material is put into maturation tub curing 15d.
11st, material in maturation tub is dried at 107 DEG C after 15d, smashes into compound nitrogen phosphate fertilizer base-material, its content is：
P2O510%th, N4%.Heavy metal：Cr3mg/kg、Cd0.2mg/kg、Pb0.05mg/kg、Hg0mg/kg、As0.21mg/kg.See inspection
Observe and predict announcement 3.Inventor carries out content of beary metal detection simultaneously to the waste water after process, and above heavy metal component is not detected, said
Bright compound nitrogen phosphate fertilizer base-material is effectively complexed with heavy metal in maturing process, and the waste water and dregs heavy metal free composition Jing after processing is dirty
Dye.And the content of beary metal of the compound nitrogen phosphate fertilizer base-material kind obtained by showing in 3 data of survey report reach fertilizer product without
Evilization index (national standard, professional standard).
The every effective substance result of attached embodiment 1 below.
1 survey report 1 of table
| Sampling observation sample | Sample quality | Fe contents % |
| Iron oxide red breeze | 50 | 35 |
2 survey report 2 of table
| Sampling observation sample | Sample quality | Manganese content % |
| Carbonic acid manganic concerntrate | 50 | 31.0 |
3 survey report 3 of table
Embodiment two
1st, leaching filter-press residues 1000g is weighed, " Section 8 " circulation 2/3 water of bucket in example () is measured, is put into disintegrating machine
Smashing is made into ore pulp, and crosses 100 eye mesh screens, and screenings enters chemical combination agitator, and oversize enters minigrinder and adds precedent
" Section 8 " circulation bucket remainder water together grind, afterwards 100 eye mesh screen of full mistake and with add chemical combination agitator, start mixer with
65 turns/min mixing speeds are stirred.
2nd, measure 98%H2SO4500ml, in adding chemical combination agitator while stirring, it is 1.0 to continue stirring 4h measurement pH values,
Terminate stirring.
3rd, filter separation of solid and liquid：Filter residue puts adapted well, and filtrate is put into neutralizing hydrolysis agitator, starts mixer, with 65 turns/
Min mixing speeds are stirred.
4th, (NH is slowly added to while stirring4)2CO3Powder, once neutralizes, and measures solution pH value, when PH is 4.5, stops adding
Enter (NH4)2CO3Powder, continues stirring and produces to bubble-free, terminate stirring.
5th, separation of solid and liquid is filtered, filtrate is put into neutralization precipitation agitator, and filter residue clear water is washed three times, and washings are together put
Enter neutralization precipitation agitator, wash the iron oxide red breeze of filter residue drying 200gFe content 41% at 107 DEG C, see examining report
4。
6th, neutralization precipitation agitator mixer is started, and is stirred with 65 turns/min mixing speeds, added while stirring
(NH4)2CO3Powder, secondary neutralization, while test solution pH value, when PH is 7.5, stops adding (NH4)2CO3Powder,
Continue stirring to produce to bubble-free, terminate stirring.
7th, separation of solid and liquid is filtered, filtrate is put in neutralization agitator, and filter residue clear water is washed three times, and cleaning solution is put in the lump
Neutralization agitator, filter residue drying 150g at 107 DEG C, the carbonic acid manganic concerntrate of Mn contents 38.8% are shown in examining report 5.
8th, neutralization agitator mixer is started, and is stirred with 65 turns/min mixing speeds, add 98% while stirring
H2SO4Solution, while test solution pH value, when PH is 7, stops adding 98%H2SO4, continue stirring and produce to bubble-free, eventually
Only stir, and liquid is put in circulation bucket in case lower circulation is used.
9th, the filter residue for measuring liquid 2L and " Section 3 " in " Section 8 " circulation bucket is put into disintegrating machine and smashes into ore pulp, plus
Enter in the hybrid reaction bucket of example (one) " Section 9 ", start agitator, and be stirred with 65 turns/min rotating speeds.
10th, weigh containing P2O5For the ground phosphate rock 1000g that 30%, SiO2 is 3.42%, in adding hybrid reaction agitator, stir
3min is mixed, then measures 98%H2SO4Solution 500ml is slowly added in hybrid reaction bucket, and stirring 15min stops stirring.Mixing is anti-
In answering bucket, material is put into maturation tub curing 12d.
11st, material in maturation tub is dried at a temperature of 107 DEG C after 12d and smashes into compound nitrogen phosphate fertilizer base-material, its content is
See examining report 6.
The every effective substance result of attached embodiment 2 below.
4 survey report 4 of table
| Sampling observation sample | Sample quality | Fe contents % |
| Iron oxide red breeze | 50 | 41 |
5 survey report 5 of table
| Sampling observation sample | Sample quality | Manganese content % |
| Carbonic acid manganic concerntrate | 50 | 38 |
6 survey report 6 of table
Embodiment three
1st, leaching filter-press residues 1000g is weighed, 2/3 water in " example (two) Section 8 " circulation bucket is measured, is put into disintegrating machine
Smashing is made into ore pulp, and crosses 100 eye mesh screens, and screenings enters chemical combination agitator, and oversize is circulated with " example (two) Section 8 "
In bucket, remaining water adds minigrinder to be ground in the lump, through 100 eye mesh screens and adds chemical combination agitator entirely afterwards.Start
Mixer is stirred with 65 turns/min mixing speeds.
2nd, measure 98%H2SO4, in adding chemical combination agitator while stirring, continuing stirring 4h, measurement pH value is 0.5, is terminated
Stirring.
3rd, filter separation of solid and liquid, filter residue is put well standby, and filtrate is put into neutralizing hydrolysis agitator, start mixer with 65 turns/
Min mixing speeds are stirred.
4th, it is slowly added to containing NH while stirring330% ammoniacal liquor, once neutralizes, while test solution pH value, when PH is 5
When, stop adding ammoniacal liquor, continue stirring and produce to bubble-free, terminate stirring.
5th, separation of solid and liquid is filtered, filtrate is put into neutralization precipitation bucket, and filter residue clear water washs three times, during washings are together put into
In settling box, filter residue drying 284g at 107 DEG C is washed, Fe contents are 45% iron oxide red breeze, see examining report 7.
6th, start neutralization precipitation agitator mixer and be stirred with 65 turns/min mixing speeds, it is slow while stirring to add
Enter containing NH330% ammoniacal liquor, secondary neutralization, while test solution pH value, when pH value is 8, stops adding ammoniacal liquor, continues stirring
Produce to bubble-free, terminate stirring.
7th, separation of solid and liquid is filtered, filtrate is put in neutralization agitator, and filter residue clear water is washed three times, and cleaning solution is added in the lump
In neutralization agitator.Washing filter residue drying 155g at 107 DEG C, Mn contents are 34.0% Mn (OH)2Concentrate, is shown in detection
Report 8.
8th, start neutralization agitator mixer and be stirred with 65 turns/min mixing speeds, be slowly added to while stirring
98%H2SO4, while test solution pH value, when pH value is 7, stops adding 98%H2SO4, continue stirring and produce to bubble-free
When terminate stirring, and liquid be put into circulation bucket in case lower recycling.
9th, liquid 2L in " Section 8 " circulation bucket is measured, and disintegrating machine is put into the filter residue of " Section 3 " and is smashed into ore pulp,
In adding the hybrid reaction bucket of " example () the 9th ", start mixer and be stirred with 65 turns/min mixing speeds.
10th, weigh containing P2O5For 30%, SiO2For 3.42% ground phosphate rock 1000g, stir in adding hybrid reaction bucket
3min, then measure 98%H2SO4500ml is slowly added in hybrid reaction bucket, stops stirring during 15min.Thing in hybrid reaction bucket
Material is put into maturation tub curing 15d.
11st, start neutralization agitator mixer and be stirred with 65 turns/min mixing speeds, add ammoniacal liquor while stirring,
PH value is measured simultaneously, when pH value is 6.5, stops adding ammoniacal liquor, continue to terminate stirring when stirring to bubble-free is produced, and liquid
During body is put into circulation bucket, following circulation is standby.
The material after 15d will have been cured in maturation tub smashing has been dried at 107 DEG C and obtained final product compound nitrogen phosphate fertilizer base-material, as a result seen
Survey report 9.
7 survey report 7 of table
| Sampling observation sample | Sample quality | Fe contents % |
| Iron oxide red breeze | 50 | 45 |
8 survey report 8 of table
| Sampling observation sample | Sample quality | Manganese content % |
| Carbonic acid manganic concerntrate | 50 | 34.0 |
9 survey report 9 of table
Claims (2)
1. a kind of method that manganese industry production waste residue is recycled, it is characterised in that：Concrete technology is as follows：（1）Filter residue is pre-processed；
（2）Acid adding is leached；（3）Slurry filtration and separation of solid and liquid；（4）Iron oxide red breeze is reclaimed；（5）Carbonic acid manganic concerntrate is reclaimed；（6）Nitrogen phosphorus is multiple
It is prepared by Hefei base-material；
Filter residue pretreatment is that filter residue first to add water crush after mixing as ore pulp, after being then classified by spiral classifier again,
Make not cross the ore particle Jing wet ball mills fine grinding of 100 mesh sieves until crossing 100 mesh sieves；
It is in ore pulp, add the concentrated sulfuric acid to make Fe that the acid adding is leached3+、Mn2+Leached in ore pulp with ionic condition；
The slurry filtration and separation of solid and liquid are to squeeze into filter press with wear-resisting resistance to acid attack Pulp pump to carry out separation of solid and liquid, gained filter cake
Peroxophosphoric acid calcareous fertilisers use is done, gained filtrate is into the process of lower step operation；
It is in step that the iron oxide red breeze is reclaimed（3）Once neutralize in prepared filtrate, add ammonium alkali pH to be adjusted to 4-5, make Fe
(OH)3Precipitation, Jing filter press press filtrations, gained Washing of Filter Cake dry to obtain iron oxide red breeze；
The ammonium alkali is ammonium hydrogen carbonate or ammonium carbonate；
It is in step that the carbonic acid manganic concerntrate is reclaimed（4）Secondary neutralization in prepared filtrate, adds ammonium alkali and adjusts pH7.2-8, make
MnSO4Precipitation, filter press press filtration separation of solid and liquid, gained Washing of Filter Cake dry to obtain carbonic acid manganic concerntrate, and gained filtrate uses dense sulphur
It is 7 that acid is neutralized to pH, sends cycling use of water pond back to；
Prepared by the compound nitrogen phosphate fertilizer base-material concretely comprises the following steps：
1. by step（3）In obtained filter cake recirculated water be ground into slurry in pulverizer, be put into slurry bucket；
2. add P2O5Content is >=26% not fluorine-containing ground phosphate rock stirring is made into slurry, into mixing reactor, standby；
3. add concentrated sulfuric acid hybrid reaction 3-5min of weight concentration more than 90%, after the completion of flow into the reaction of belt formation chamber
30min；
4. aerobic fermentation tank curing 7-15d is sent into, dries pulverizing obtains final product compound nitrogen phosphate fertilizer base-material.
2. the method that manganese industry production waste residue according to claim 1 is recycled, it is characterised in that：When the acid adding is leached
The concentrated sulfuric acid is added, pH≤1.5 are controlled.
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| CN103204743B (en) * | 2013-04-26 | 2015-03-25 | 赵阳臣 | Method and equipment for producing slow-release compound fertilizer from manganese ore tailings |
| CN103555959B (en) * | 2013-11-07 | 2015-02-25 | 广西桂柳化工有限责任公司 | Technology for comprehensively recycling leaching residue in production of electrolytic manganese metal and manganese dioxide |
| CN103789551B (en) * | 2014-02-18 | 2016-01-20 | 广西大学 | Prepare manganese sulfate electrolyte with electrolytic manganese anode mud and reclaim plumbous method |
| CN103820647B (en) * | 2014-03-22 | 2015-07-01 | 重庆大学 | Method for secondary leaching of electrolytic manganese residue and manganese recovery |
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Effective date of registration: 20170912 Address after: Xinxian County the Guangxi Zhuang Autonomous Region village 532315 Chongzuo City Lei Zhen Zhi Tun Da Ban under the letter of the Xinxian County Manganese Mining Co. Ltd. Patentee after: Xinxian County great faith Manganese Mining Co., Ltd. Address before: Xinxian County the Guangxi Zhuang Autonomous Region village 532315 Chongzuo City Lei Zhen Zhi Tun Da Ban under the letter of the Xinxian County Manganese Mining Co. Ltd. Patentee before: Zhao Yangchen |
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