CN105036197A - Method for preparing high purity manganese carbonate - Google Patents
Method for preparing high purity manganese carbonate Download PDFInfo
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Abstract
The invention provides a method for preparing high purity manganese carbonate. According to the method, a manganese solution prepared from industrial manganese sulfate or manganese chloride is adopted as the raw material. The method comprises the following steps: (1) preparing a manganese sulfate solution; (2) removing heavy metals; (3) preparing crude filter liquor; (4) preparing refined filter liquor I: carrying out refined filtration on the crude filter liquor to obtain the refined filter liquor I; (5) complexing calcium and magnganese: adding a calcium and magnganese complexing agent into the refined filter liquor I; (6) preparing high purity manganese carbonate: obtaining a manganese carbonate solution, and carrying out dehydration, washing and drying to obtain a high purity manganese carbonate product. According to the method, the defects of the conventional technology are overcome, the manganese carbonate content of the produced manganese carbonate is 99% or above, and the content of each of the heavy metals like potassium, sodium, calcium, magnesium, and ferrum is not larger than 10 ppm; fluoride is not used, so that environmental pollution is avoided; the method is simple in technology and low in cost.
Description
Technical field:
That the present invention relates to is a kind of preparation method, particularly a kind of method preparing high-purity manganese carbonate of carbonate.
Technical background:
Manganous carbonate manufactures telecommunication equipment soft magnetic ferrite, the important source material of synthesis Manganse Dioxide and other manganese salt of manufacture, and be used as the catalyzer of desulfurization, the pigment of enamel, coating and varnish.At present, the manganous carbonate of China is primarily of the useless manganese liquid produced during Process of Hydroquinone Production through neutralization, and decolouring, removal of impurities, carbonization preparation and obtaining, because its purity is low, containing benzene class toxic substance, makes its application in industry be very restricted.With low-grade manganese ore through acidleach, removal of impurities, manganous carbonate prepared by carbonization, product is not containing organism, and heavy metal content is low, can meet the requirement of feed grade and electronic grade product.Then, manganous carbonate prepared by this manganese ore, its potassium sodium calcium-magnesium content is higher, and particularly calcium-magnesium content is difficult to reach below 100ppm.
Manganous carbonate is as a kind of important intermediate of manganese salt, and manganous carbonate, after corresponding acidifying, can prepare manganous sulfate, manganous nitrate, manganous acetate, the manganese salt such as Manganous chloride tetrahydrate, after pyroprocessing, can preparative chemistry Manganse Dioxide, and manganic oxide, trimanganese tetroxide.The quality of purity to product of oxide spinel manganese plays a part very crucial aborning, at present, for the manganous sulfate of cell-grade, Manganse Dioxide, the trimanganese tetroxide of ferroxcube magnet and the manganous nitrate of SILVER REAGENT, Manganous chloride tetrahydrate, manganous acetate, all very harsh to the requirement of calcium magnesium, particularly SILVER REAGENT, require that calcium magnesium can control within 20ppm, this is very high to the purity requirement of manganous carbonate.
For obtaining high-purity manganous carbonate, must make manganese liquid before carbonization the removing of calcium magnesium, existing calcium-magnesium removing method is generally add villiaumite or abstraction impurity removal.Excessive more than 1 to 3 times of the villiaumite that the processing requirement adding villiaumite adds, therefore, will inevitably make product introduce fluorine impurity, and the Calcium Fluoride (Fluorspan) generated, magnesium fluoride granularity is meticulous, is difficult to filter, add the control difficulty of technique, the manganous carbonate calcium magnesium produced after purification can only control within 50ppm; There is production process complexity in abstraction impurity removal, the shortcoming that cost is high.
For another Chinese Patent Application No. be 00113535.X " a kind of manufacture method of high-purity manganese carbonate " its be for raw material with pyrolusite and rhodochrosite, fluorochemical is added with after sulfuric acid to leach, the calcium of solubility, magnesium ion are precipitated, then reacts high-purity manganese carbonate processed with volatile salt.Adopt the method, maximum shortcoming is the use of fluorochemical, and to environmental requirement more and more stricter today, the pollution of fluorochemical to environment is increasing, and extremely difficult; On the other hand, the method only effectively can be removed calcium ions and magnesium ions, and to the heavy metal ion in other raw materials as lead, arsenic, cadmium, copper, cobalt, nickel, zinc, chromium then can not effectively be removed; The purity of its manganous carbonate produced does not reach high-purity requirement equally like this;
Simultaneously another Chinese Patent Application No. be 200810048432.4 " method with preparing high-purity manganese carbonate with pyrolusite " its be add the manganese sulfate solution of aniline through sulfuric acid leaching for raw material with pyrolusite, add villiaumite calcium-magnesium removing, add flocculation agent and oxygenant simultaneously, after sulfide etc. removing heavy metals, obtain high-purity manganese carbonate through carbonization.Adopt the method, calcium-magnesium removing is also adopt fluorochemical, still there is fluorion and have pollution to environment, and extremely unmanageable shortcoming, because the chemical composition added is too much, so just cause and need the ion thing that will remove the manganous carbonate of required purification to be just difficult to remove totally, the manganous carbonate therefore using the method to produce can only reach the standard of HG/T2836-1997I, and calcium ions and magnesium ions cannot be less than the level of 10ppm.
Summary of the invention:
The invention provides a kind of method preparing high-purity manganese carbonate, which overcome the deficiency of existing Technology, the content more than 99.0% of the manganous carbonate produced, and the potassium in high-purity manganese carbonate product, sodium, calcium, magnesium, the heavy metals such as iron are not all higher than 10ppm; And do not use fluorochemical, can not to environment; Production technique is simple, and production cost is low.
1, a kind of method preparing high-purity manganese carbonate of the present invention, the manganese solution be mixed with industrial manganic sulfate or Manganous chloride tetrahydrate is raw material, comprises following processing step:
(1) Sulphuric acid manganese solution, the concentration controlling manganese metal in raw material manganese solution is 50g/L-150g/L;
(2) removing heavy metals, adds sodium sulphite and carries out removing heavy metals in the manganese solution of (1) step, and the pH value controlling solution is 3.5-7.0, stirs, and leaves standstill and filters to get filtrate 1;
(3) coarse filtration liquid processed, by the pH regulator of filtrate 1 to 2.5-5.0, temperature controls, at 25 DEG C-90 DEG C, to add oxalate solution, the quality that control oxalate adds is the 100-500% of deliming theoretical amount, and stir, adjusted to ph is to 5.5-7.0, stir again, leave standstill, filter to obtain coarse filtration liquid;
(4) make smart filtrate 1, by coarse filtration liquid after essence is filtered, obtain smart filtrate 1;
(5) complexing calcium magnesium, adds calcium magnesium complexing agent in smart filtrate 1, and the add-on of complexing agent is the 100-300% of calcium magnesium mass content in smart filtrate, then the pH of smart filtrate 1 is adjusted to 4.0-6.0, obtains smart filtrate 2;
(6) high-purity manganese carbonate processed, adds ammonium hydrogencarbonate in the smart filtrate 2 of (5) step, and pH when controlling reaction is 6.5-7.2, obtains manganous carbonate solution, through dehydration, and washing, dry, obtain high-purity manganese carbonate product.
Method of the present invention, the amount that preferably control (2) step sodium sulphite adds is the 200-500Wt% of heavy metal theoretical amount in manganese solution.
Heavy metal of the present invention is lead, arsenic, cadmium, copper, cobalt, nickel, one or more in zinc, chromium.
Method of the present invention, the oxalate solution described in (3) step is sodium oxalate or ammonium oxalate solution; Preferred control ph is 2.5-5.5, and churning time is 2 hours, and time of repose is 2-8 hour.
Method of the present invention, described (4) step system essence filtrate 1 preferably adopts ultra-filtration membrane membrane filtration, ultrafiltration membrane material preferred polyamide or polycarbonate polymeric membrane for separation.Or can filtering with microporous membrane be adopted.
The present invention (5) step complexing calcium ions and magnesium ions, described calcium magnesium complexing agent is Trisodium Citrate, Sunmorl N 60S, any one or a few in phosphoric acid salt.Phosphoric acid salt as Sodium hexametaphosphate 99, sodium polyphosphate, SODIUM PHOSPHATE, MONOBASIC etc.After adding complexing agent, pH value preferably controls at 4.0-6.0, and within the scope of this pH, complexing agent has better complexing effect to calcium magnesium.
Washing described in the present invention (6) step preferably adopts pure water or deionized water; Centrifuge dehydration is adopted during dehydration.
Raw material of the present invention is outside the manganese solution using industrial manganic sulfate or Manganous chloride tetrahydrate to be mixed with, and also can adopt with manganese ore is that raw material impregnated in the manganese solution made in industrial sulphuric acid solution.
The present invention adopts aforesaid method to have following beneficial effect: 1) with oxalic acid or oxalate deliming, because caoxalate is insoluble to diluted acid, and manganous oxalate is dissolved in diluted acid, so when the pH in manganese liquid maintains under acidic conditions (when pH value is 2.5 ~ 5.0), caoxalate can first be precipitated out, after pH is transferred to neutrality, remaining oxalate can form magnesium oxalate, the precipitations such as manganous oxalate, because manganous oxalate in neutral conditions solubleness is low, remaining oxalic acid in solution can be made to remove with whole, and the manganous oxalate formed can regenerate in acid condition to be reused, remaining magnesium ion can form water-soluble Magnesium hydrogen carbonate and wash away, like this, the removal of calcium magnesium instead of the technique adding fluorochemical, avoid in finished product and carry fluorion secretly, and avoid the pollution of fluorine to environment.2) select ultra-filtration membrane essence to filter, solve the shortcoming that trickle caoxalate particle is difficult to eliminate with traditional filter method, and insoluble silicon and other insoluble impurities can be removed, greatly improve the purity of solution.3) the calcium magnesium complexing agent added, with the calcium ions and magnesium ions complexing in manganese liquid, form water-soluble complex compound, and pH is controlled between 4.0-6.0, within the scope of this pH, complexing agent has better complexing effect to calcium magnesium, reduce further manganese liquid with the calcium magnesium carried secretly into during the synthesis of carbon ammonium, improve the purity of product.4) being can by heavy metal ion lead described above in raw material, arsenic, cadmium, copper, cobalt, nickel, and zinc, chromium are effectively removed.The manganous carbonate purity produced is high, the potassium in product, sodium, calcium, magnesium, and iron and heavy metal be not higher than 10ppm, and quality product can meet SILVER REAGENT requirement.
The main chemical equation that above-mentioned preparation method of the present invention relates to and cardinal principle comprise as follows:
MSO42-+S2-＝MS↓，
C2O42-+Ca2+＝CaC2O4↓，
C2O42-+Mn2+＝MnC2O4↓，
Wherein, M is metal ion, can be plumbous, arsenic, cadmium, copper, cobalt, nickel, zinc, one or more in chromium;
In above-mentioned preparation method, described removal of impurities theoretical amount is the cleaner consumption calculated according to the foreign matter content in the material solution measured in advance and above chemical principle, its method of calculation and computation process are undertaken by existing method, disclosed in being namely to those skilled in the art.
Embodiment: the present invention is described in further detail below in conjunction with specific embodiment.
A kind of method preparing high-purity manganese carbonate of the present invention, concrete grammar is:
1. being mixed with manganese sulfate solution or industrial chlorinations manganese with industrial manganic sulfate, to be configured to manganese chloride solution be raw material, and the concentration of above manganese metal content is 50g/L ~ 150g/L, and detection method generally tests the content of its calcium magnesium and heavy metal by atomic absorption;
2. in filtrate, add sodium sulphite solid removing heavy metals, the amount added controls at the 200%-500% for theoretical amount, and pH value controls between 3.5-7.0, stirs after 2 hours and leaves standstill filtration, obtain filtrate 1;
3. between the pH regulator of the filtrate 1 in above-mentioned steps 2 to 2.5-5.5, temperature controls at 25 DEG C-90 DEG C, then sodium oxalate or ammonium oxalate solution is added, add-on is the 150%-500% of calcium-magnesium removing theoretical amount, stir after 2 hours, add manganous carbonate and pH value is adjusted between 5.5-7.0, then stir after 2 hours leave standstill 2 to 8 hours, filter, obtain coarse filtration liquid.
4. the rough filtrate in step 3 is carried out essence through ultra-filtration membrane to filter, elimination caoxalate and manganous oxalate etc. and other solia particle, the polymeric membrane for separation such as ultrafiltration membrane material preferred polyamide or polycarbonate, obtain smart filtrate 1;
5. in the smart filtrate 1 in step 4, add calcium magnesium complexing agent, complexing agent is Trisodium Citrate, Sunmorl N 60S, any one or a few in phosphoric acid salt, the add-on of complexing agent is the 100%-300% of calcium in solution, magnesium mass content, then pH is adjusted between 4.5 to 6.0, the smart filtrate 2 after calcium, magnesium must be removed;
6. by the smart filtrate 2 of the calcium-magnesium removing in step 5 or be manganese liquid, with ammonium hydrogencarbonate reaction, when pH reaches 6.5-7.5, stopped reaction, obtains manganous carbonate solution, then by the manganous carbonate of synthesis through centrifuge dehydration, and with pure water, drying, obtains high-purity manganese carbonate product.
In the following embodiments except the explanation in embodiment, all the other undeclared parts are all identical with above-mentioned embodiment.Its calcium ions and magnesium ions of the high-purity manganese carbonate utilizing the inventive method to prepare is less than the level of 10ppm.
Embodiment 1:
(1): by purity be 98% 500g technical grade manganous sulfate water-soluble, be settled to the manganese sulfate solution that 2000ml is configured to Fe content 79.5g/L after dissolving completely, with the content of atomic absorption test calcium, magnesium and heavy metal wherein;
(2): in step (1) manganese sulfate solution, add sodium sulphite 0.98g, then the pH of solution is adjusted to 6.0, stir after 2 hours and filter, obtain filtrate 1;
(3): the solution after step (2) being filtered and the pH of filtrate 1 are adjusted to 3.0, the ammonium oxalate that 4.24g has dissolved is added after being heated to 50 DEG C, stir after 2 hours, with manganous carbonate, the pH of filtrate 1 is adjusted to 6.5, after stirring 2 hours again, leave standstill 6 hours, filtering solution and filtrate 1 are coarse filtration liquid;
(4): the solution after step (3) is filtered and coarse filtration liquid, squeeze into ultra-filtration membrane with pump, filter caoxalate, magnesium oxalate and manganous oxalate particulate and other solia particle, obtain smart filtrate 1;
(5): add 0.98g Trisodium Citrate in the solution after filtering toward step (4) and smart filtrate 1, after stirring, the pH of solution is modulated 5.0, leave standstill, obtain smart filtrate 2;
(6): in the solution essence filtrate 2 in step (5), add the ammonium bicarbonate solution configured, and open stirring reaction, when the pH of control reaction soln reaches 6.5, stop stirring, gained solution will be reacted, through centrifuge dehydration, and use pure water repetitive scrubbing, drying, obtains high-purity manganese carbonate product of the present invention.
The material solution that the present embodiment 1 uses and the stoste described in table 1, each metal content data are as following table 1; Table 2, each composition detection result in the high-purity manganese carbonate product prepared for utilizing the inventive method, high-purity manganese carbonate finished product data;
Table 1:
| Element | Calcium (g/L) | Magnesium (g/L) | Zinc (g/L) | Copper (g/L) | Plumbous (g/L) | Cadmium (g/L) | Manganese (g/L) |
| Stoste | 0.35 | 0.195 | 0.075 | 0.025 | 0.012 | 0.01 | 79.65 |
| After removing heavy metals | 0.348 | 0.194 | 0.0008 | 0.0002 | 0.0004 | 0.0003 | 79.52 |
| After deliming | 0.0030 | 0.061 | 0.0008 | 0.0002 | 0.0004 | 0.0003 | 79.38 |
Illustrate: stoste described in table 1 is for the manganese sulfate solution described in the present invention (1) step or for manganese containing solution; After removing heavy metals, refer to the content of the solution of the manganese sulfate solution of (1) step after the removing heavy metals of (2) step and each metal in filtrate 1; In like manner refer to the content of each metal in filtrate 1 solution that essence is filtered after (3) step deliming and smart filtrate 1 after deliming.Data below in embodiment are similar successively.
Table 2:
Illustrate: be the detection data of the high-purity manganese carbonate that utilizes the inventive method to prepare in table 2, detection method is undertaken by the detection method of prior art; Sulfate radical in table refers to sulfate ion, and chlorine root refers to chlorion.
Embodiment 2:
(1): by purity be 98% 1000kg industrial manganic sulfate water-soluble, completely dissolve after be settled to 2.2M
3be configured to the solution of manganese content 144.5g/L, test the content of its calcium magnesium and heavy metal by atomic absorption;
(2): in step (1) solution, add sodium sulphite 3.58kg, then the pH of solution is adjusted to 6.5, stir after 2 hours and filter.
(3): the pH value of solution after step (2) being filtered is adjusted to 3.5, adds the sodium oxalate that 9.84kg has dissolved, stir after 2 hours, with manganous carbonate, pH is adjusted to 7.0 after being heated to 65 DEG C, then to stir after 2 hours standing 5 hours, filtering solution.
(4): ultra-filtration membrane squeezed into by the solution pump after step (3) being filtered, and filters caoxalate, magnesium oxalate and manganous oxalate particulate and other solia particle.
(5): add 1.21kg Sodium hexametaphosphate 99 in the solution after filtering toward step (4), after stirring, the pH of solution is modulated 4.5, leave standstill.
(6): the solution in step (5) is added the ammonium bicarbonate solution configured, and open stirring, when pH reaches 7.0, stop stirring, by reaction solution centrifuge dehydration, and use pure water repetitive scrubbing, dry, obtain high-purity manganese carbonate product.
Table 3:
Illustrate: in table 3, each data are detect data in embodiment 2.
Table 4:
Illustrate: the data in table 4 are detect data in embodiment 2.
Embodiment 3:
(1): after water-soluble for 350.8 ㎏ technical grade Manganese chloride anhydrous, be settled to 2M
3, test the content of its calcium, magnesium and heavy metal by atomic absorption, it is 75g/L that chemical titration surveys its manganese metal content;
(2): in step (1) solution, add sodium sulphite 1.32kg, then the pH of solution is adjusted to 7.0, stir after 2 hours and filter;
(3): the pH value of solution after step (2) being filtered is adjusted to 4.0, adds the ammonium oxalate that 9.702kg has dissolved, stir after 2 hours, with manganous carbonate, pH is adjusted to 6.5 after being heated to 55 DEG C, then to stir after 2 hours standing 5 hours, filtering solution;
(4): ultrafiltration membrance filter squeezed into by the solution pump after step (3) being filtered, and filters caoxalate, magnesium oxalate and manganous oxalate particulate and other solia particle;
(5): add 1.15kg Sunmorl N 60S in the solution after filtering toward step (4), after stirring, the pH of solution is modulated 4.5, leave standstill;
(6): the solution in step (5) is added the ammonium bicarbonate solution configured, and unlatching stirring, when the pH of reaction soln reaches 7.2, stop stirring, by the manganous carbonate centrifuge dehydration of making, and use pure water repetitive scrubbing, drying, obtains high-purity manganese carbonate product.
Table 5:
Data in table 5 are detect data in embodiment 3.
Table 6:
Data in table 6 are detect data in embodiment 3.
Claims (6)
1. prepare a method for high-purity manganese carbonate, the manganese solution be mixed with industrial manganic sulfate or Manganous chloride tetrahydrate is raw material, comprises following processing step:
(1) manganese solution processed, the concentration controlling raw material manganese solution is 50g/L-150g/L;
(2) removing heavy metals, adds sodium sulphite and carries out removing heavy metals in the manganese solution of (1) step, and the pH value controlling solution is 6.0 ~ 7.0, stirs, and leaves standstill and filters to get filtrate 1;
(3) coarse filtration liquid processed, by the pH regulator of filtrate 1 to 2.5-4.5, temperature controls, at 25 DEG C ~ 70 DEG C, to add oxalate solution, the quality that control oxalate adds is the 150-500% of deliming theoretical amount, and stir 1-3 hour, adjusted to ph is to 5.5-7.0, stir again, leave standstill, filter to obtain coarse filtration liquid;
(4) make smart filtrate 1, by rough filtrate after essence is filtered, obtain smart filtrate 1;
(5) calcium-magnesium removing ion, complexing calcium magnesium, adds calcium magnesium complexing agent in smart filtrate 1, and the add-on of complexing agent is the 100-300% of calcium magnesium mass content in smart filtrate, then the pH of smart filtrate 1 is adjusted to 4.0-6.0, obtains the smart filtrate 2 of calcium-magnesium removing;
(6) high-purity manganese carbonate processed, adds ammonium hydrogencarbonate in the smart filtrate 2 of (5) step, and pH when controlling reaction is 6.5-7.5, obtains manganous carbonate solution, through dehydration, and washing, dry, obtain high-purity manganese carbonate product.
2., according to the method preparing high-purity manganese carbonate according to claim 1, it is characterized in that controlling the 200-500Wt% that the amount that adds of (2) step sodium sulphite is heavy metal theoretical amount in manganese solution.
3. according to the method preparing high-purity manganese carbonate described in claim 1 or 2, it is characterized in that described heavy metal is lead, arsenic, cadmium, copper, cobalt, nickel, one or more in zinc, chromium.
4., according to the method preparing high-purity manganese carbonate according to claim 1, it is characterized in that the oxalate solution described in (3) step is sodium oxalate or ammonium oxalate solution; Controlling churning time is 2 hours, and time of repose is 2-8 hour.
5., according to the method preparing high-purity manganese carbonate according to claim 1, it is characterized in that described (4) step system essence filtrate 1 adopts ultra-filtration membrane membrane filtration.
6. according to the method preparing high-purity manganese carbonate according to claim 1, it is characterized in that (5) step complexing calcium magnesium, described calcium magnesium complexing agent is Trisodium Citrate, Sunmorl N 60S, any one or a few in phosphoric acid salt.
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| CN110316760A (en) * | 2019-07-29 | 2019-10-11 | 佛山西陇化工有限公司 | A kind of preparation method of ultra-fine manganese carbonate |
| CN111908510A (en) * | 2019-05-16 | 2020-11-10 | 清华大学 | Preparation method of high-purity manganese sulfate |
| CN112875758A (en) * | 2021-01-25 | 2021-06-01 | 浙江中金格派锂电产业股份有限公司 | Preparation method of low-cost high-capacity lithium manganate precursor |
| CN113860376A (en) * | 2021-11-04 | 2021-12-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity manganese carbonate by using vanadium extraction wastewater |
| CN114368785A (en) * | 2022-01-07 | 2022-04-19 | 重庆民丰化工有限责任公司 | Process for removing impurities in sodium bichromate production |
| CN114715943A (en) * | 2022-03-28 | 2022-07-08 | 中南大学 | Process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride and preparation method |
| CN115784169A (en) * | 2022-08-31 | 2023-03-14 | 平利县安得利新材料有限公司 | Purification method of sodium sulfide crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109319844A (en) * | 2018-12-07 | 2019-02-12 | 贵州大龙汇成新材料有限公司 | A kind of Impure Manganese-Sulfate method of purification |
| CN111908510A (en) * | 2019-05-16 | 2020-11-10 | 清华大学 | Preparation method of high-purity manganese sulfate |
| CN111908510B (en) * | 2019-05-16 | 2021-06-29 | 清华大学 | Preparation method of high-purity manganese sulfate |
| CN110316760A (en) * | 2019-07-29 | 2019-10-11 | 佛山西陇化工有限公司 | A kind of preparation method of ultra-fine manganese carbonate |
| CN112875758A (en) * | 2021-01-25 | 2021-06-01 | 浙江中金格派锂电产业股份有限公司 | Preparation method of low-cost high-capacity lithium manganate precursor |
| CN113860376A (en) * | 2021-11-04 | 2021-12-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity manganese carbonate by using vanadium extraction wastewater |
| CN114368785A (en) * | 2022-01-07 | 2022-04-19 | 重庆民丰化工有限责任公司 | Process for removing impurities in sodium bichromate production |
| CN114715943A (en) * | 2022-03-28 | 2022-07-08 | 中南大学 | Process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride and preparation method |
| CN115784169A (en) * | 2022-08-31 | 2023-03-14 | 平利县安得利新材料有限公司 | Purification method of sodium sulfide crystal |
| CN115784169B (en) * | 2022-08-31 | 2023-11-24 | 平利县安得利新材料有限公司 | Purification method of sodium sulfide crystal |
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Application publication date: 20151111 |