CN102249342B - Method for producing potassium manganite or sodium manganate - Google Patents
Method for producing potassium manganite or sodium manganate Download PDFInfo
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- CN102249342B CN102249342B CN2011101621763A CN201110162176A CN102249342B CN 102249342 B CN102249342 B CN 102249342B CN 2011101621763 A CN2011101621763 A CN 2011101621763A CN 201110162176 A CN201110162176 A CN 201110162176A CN 102249342 B CN102249342 B CN 102249342B
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Abstract
The invention belongs to the field of production of potassium (sodium) manganite. In the method, a mixed calcining material of manganese mineral powder and potassium (sodium) hydrate is oxidized by using an oxidizing gas, and the potassium (sodium) manganite is produced intermittently by adopting a gas-solid fluidized bed reactor. The method comprises the following steps of: (1) adding potassium (sodium) hydrate into manganese mineral powder serving as a raw material, stirring and calcining to obtain sintering charge; (2) milling the obtained sintering charge; (3) adding the obtained powder into the gas-solid fluidized reactor, introducing the oxidizing gas, regulating the ventilation amount to keep the powder to be in a fluidized state, keeping the temperature in the reactor to be between 220 DEG C and 300 DEG C, and reacting for 0.5-3 hours to obtain a potassium (sodium) manganite product; and (4) dissolving, stirring and standing the sintering product, performing solid-liquid separation to obtain a liquid phase which is a potassium (sodium) manganite solution and a solid phase which is unreacted manganese ore, and returning to the step (1). The method has the advantages of short process flow, simple equipment, high oxidation speed, short production period and capability of remarkably increasing the transformation rate of potassium (sodium) manganite.
Description
Technical field
The invention belongs to the production technical field of potassium manganate (sodium), utilize oxidizing gas that the baking mixed material of manganese ore powder and potassium hydroxide (sodium) is carried out oxide treatment, adopt the method for gas-solid fluidized bed reactor batch production potassium manganate or sodium manganate.
Background technology
Potassium manganate (sodium) is a kind of important Chemicals, is to produce the intermediate product that must experience in potassium permanganate or the sodium permanganate process, because it has strong oxidizing property, is widely used in the industries such as organic synthesis, medical and health, petrochemical complex, water treatment.
The production of potassium manganate (sodium) mainly is take manganese oxide ore as raw material, reacts with potassium hydroxide (sodium) in well-oxygenated environment and realizes.Its preparation technology can be divided into solid-state roasting method and liquid phase oxidation two classes.Solid-state roasting method exploitation is morning, and technical maturity is simple; But there are the problems such as energy consumption height, work under bad environment, production cycle length, low conversion rate in it.Liquid phase oxidation is technology newly developed in recent years, and it is poor that it has overcome the solid phase method production environment, and the problem that the cycle is long has the transformation efficiency height, the advantage that energy consumption is low, and can process the manganese ore that manganese content is slightly low, the silicon amount is slightly high.But because alkali manganese ratio is high, at high temperature corrodibility is strong, and is higher to equipment requirements.
Chinese patent 200810056602.3 discloses a kind of method of producing potassium manganate, at high temperature with oxygen-containing gas the compound of manganese ore powder and potassium hydroxide solution is carried out the gas and liquid flowing oxide treatment, although shortened the reaction times, reduce the consumption of alkali, but needed the reactor upper pressure of 0.2 ~ 0.5MPa.
Chinese patent 200910178460.2 provides a kind of method of continuous production of potassium manganate, at first potassium hydroxide solution is mixed with the manganese ore powder, adds initiator, is modulated into slip, supplies to high pressure vessel and reacts.The method can be processed the lower manganese ore of grade, and the reaction times significantly shorten, prepared using is abundant.But the alkali manganese mol ratio that needs 1:9 ~ 13, the oxygen of 0.7 ~ 1.2MPa is pressed, to having relatively high expectations of equipment.
More than two kinds of methods all need under condition of high voltage, react, device structure and compressive property are had relatively high expectations, in addition, existing patent has only been introduced the technique of utilizing manganese oxide ore to produce potassium manganate (sodium), and is also inapplicable than the manganese carbonate ore resource of horn of plenty for China.
Summary of the invention
The purpose of this invention is to provide a kind of method of producing potassium manganate or sodium manganate, utilize oxidizing gas that the baking mixed material of manganese ore powder and potassium hydroxide or sodium hydroxide is carried out oxide treatment, adopt gas-solid fluidized bed reactor batch production potassium manganate or sodium manganate under normal pressure, the significant oxidation time that shortens, the consumption of reduction alkali.
A kind of method of producing potassium manganate or sodium manganate comprises the steps:
(1) take the manganese ore powder as raw material, add potassium hydroxide or sodium hydroxide, put into stoving oven after fully stirring, at 300 ~ 850 ℃ of lower sintering 0.5 ~ 2h; , the content of manganese is 20%～63% in the described manganese ore powder, the granularity of manganese ore powder accounts for more than 70% for-200 orders; Manganese ore powder and potassium hydroxide or sodium hydroxide manganese alkali mol ratio are
1：2~3.6；
(2) be 70% ~ 90% with levigate extremely-200 order content of described step (1) gained sintered material;
(3) pulverulent material that described step (2) is obtained adds gas-solid fluidized bed reactor, pass into oxidizing gas, regulating air flow makes material be in fluidized state, keep 220 ~ 300 ℃ of reactor temperatures, reaction 0.5 ~ 3h, described oxidizing gas can be air, oxygen or chlorine, and water content is 20 ~ 300g/m in its Air and the oxygen
3, the volume fraction of nitrogen, air or oxygen is 0 ~ 90% in the chlorine;
(4) potassium manganate that described step (3) is obtained or sodium manganate roasting product dissolve, stir and leave standstill 10 ~ 30min, carry out solid-liquid separation, and liquid phase is potassium manganate or sodium manganate solution, and solid phase mainly is unreacted manganese ore, return step (1) again.Amount of water is 2 ~ 5 times of roasting material during dissolving.
Wherein the powder of manganese ore described in the step 1 is manganese carbonate ore or manganese oxide ore; Described potassium hydroxide or sodium hydroxide solution mass percent concentration are 35% ~ 55%; Described abundant stirring be will the manganese ore powder and potassium hydroxide or the direct mixing of sodium hydroxide put into stoving oven after stirring, or first that potassium hydroxide or sodium hydroxide is water-soluble, the manganese ore powder is added carry out again roasting after blending together mashed prod in the solution again; Described stoving oven is open hearth or rotary kiln.
The present invention compared with prior art has the following advantages:
1, manganese ore powder raw material of the present invention can also can be manganous carbonate for manganese oxide, and raw material sources are extensive, can take full advantage of the multiple manganese resource of China.
2, the present invention adopts gas-solid fluidized bedly as reactor under normal pressure, and the sintering of material does not occur under the fluidization condition, and is lighter to the extent of corrosion of equipment; The method can be able to make fully contact between the reactant, can improve significantly rate of oxidation, thereby shorten the production cycle, improves throughput, and can improve the transformation efficiency of potassium manganate or sodium manganate.
3, the used oxidizing gas of the present invention can be air, oxygen and chlorine etc., and oxidant source is extensive.
3, the present invention need not to add+6 manganic compound initiators, has reduced production cost.
4, the present invention can produce potassium manganate and sodium manganate efficiently, has good adaptability.
Description of drawings
Fig. 1 is for producing the process flow sheet of potassium manganate (sodium).
Embodiment
Embodiment 1
(1) be that 35% pyrolusite powder is broken to-200 order content and accounts for 70% with 500g manganese content, take by weighing potassium hydroxide 392g, add 350ml water, stirring makes the potassium hydroxide dissolving, wherein alkali concn is 53%, adds the manganese ore powder and stir to form mashed prod, puts into stoving oven, at 400 ℃ of lower sintering 1h, the manganese alkali mol ratio of described pyrolusite and potassium hydroxide is 1:2.2;
(2) step (1) gained agglomerate is pulverized, made-200 order content account for 70%;
(3) the particulate fine ore in the described step (2) is put into fluidized-bed reactor, pass into air and make material be in suspended state, keeping airborne water-content is 50g/m
3, at 220 ℃ of lower oxidizing roasting 2h.
(4) roasting product in the described step (3) is dissolved, amount of water is 2 times of roasting product quality, and mixing speed is 10r/min, churning time is 10min, carry out solid-liquid separation, the gained solid phase mainly is unreacted Manganse Dioxide, and the gained liquid phase is potassium manganate solution; Among this embodiment in the pyrolusite transformation efficiency of manganese be 93.4%.
Embodiment 2
(1) be that 50% pyrolusite powder is broken to-200 order content and accounts for 72% with 500g manganese content, weighing sodium hydroxide 473g with two kinds of material stirring mixings, puts into stoving oven, and at 350 ℃ of lower sintering 1h, the manganese alkali mol ratio of described pyrolusite and sodium hydroxide is 1:2.6;
(2) step (1) gained agglomerate is pulverized, made-200 order content account for 70%;
(3) the particulate fine ore in the described step (2) is put into fluidized-bed reactor, pass into oxygen and make material be in suspended state, keeping the water-content in the oxygen is 100g/m
3, at 240 ℃ of lower oxidizing roasting 1h.
(4) roasting product in the described step (3) is dissolved, amount of water is 2.5 times of roasting product quality, and mixing speed is 10r/min, churning time is 10min, carry out solid-liquid separation, the gained solid phase mainly is unreacted Manganse Dioxide, and the gained liquid phase is sodium manganate solution; Among this embodiment in the pyrolusite transformation efficiency of manganese be 92.2%.
Embodiment 3
(1) be that 30% manganese carbonate ore is crushed to-200 order content and accounts for 75% with 650g manganese content, take by weighing potassium hydroxide 556g, add 550ml water, stirring makes the potassium hydroxide dissolving, wherein alkali concn is 50%, adds the manganese ore powder and stir to form mashed prod, puts into stoving oven, at 800 ℃ of lower sintering 1.5h, the manganese alkali mol ratio of described manganese carbonate ore and potassium hydroxide is 1:2.8;
(2) step (1) gained agglomerate is pulverized, made-200 order content account for 75%;
(3) the particulate fine ore in the described step (2) is put into fluidized-bed reactor, pass into heating chlorine and make material be in suspended state, keeping the volume fraction of nitrogen in the chlorine is 70%, at 250 ℃ of lower oxidizing roasting 1h.
(4) roasting product in the described step (3) is dissolved, amount of water is 3 times of roasting product quality, and mixing speed is 10r/min, and churning time is 15min, carries out solid-liquid separation, and the gained liquid phase is potassium manganate solution; Among this embodiment in the manganese carbonate ore transformation efficiency of manganese be 87.5%.
Embodiment 4
(1) be that 30% manganese carbonate ore is crushed to-200 order content and accounts for 77% with 650g manganese content, weighing sodium hydroxide 425g, add 440ml water, stirring makes dissolution of sodium hydroxide, wherein alkali concn is 49%, adds the manganous carbonate breeze and stir to form mashed prod, puts into stoving oven, at 850 ℃ of lower sintering 2h, the manganese alkali mol ratio of described manganese carbonate ore and sodium hydroxide is 1:3.0;
(2) step (1) gained agglomerate is pulverized, made-200 order content account for 73%;
(3) the particulate fine ore in the described step (2) is put into fluidized-bed reactor, pass into chlorine and make material be in suspended state, the volume fraction of regulating the chlorine Air is 80%, at 260 ℃ of lower oxidizing roasting 1h.
(4) roasting product in the described step (3) is dissolved, amount of water is 2.5 times of roasting product quality, and mixing speed is 10r/min, and churning time is 15min, carries out solid-liquid separation, and the gained liquid phase is sodium manganate solution; Among this embodiment in the manganese carbonate ore transformation efficiency of manganese be 89.4%.
Embodiment 5
(1) be that 38% pyrolusite powder is broken to-200 order content and accounts for 70% with 500g manganese content, take by weighing potassium hydroxide 542g, with two kinds of material stirring mixings, put into stoving oven, at 400 ℃ of lower sintering 1h, the manganese alkali mol ratio of described pyrolusite and potassium hydroxide is 1:2.8;
(2) step (1) gained agglomerate is pulverized, made-200 order content account for 72%;
(3) the particulate fine ore in the described step (2) is put into fluidized-bed reactor, pass into chlorine and make material be in suspended state, the volume fraction of regulating oxygen in the chlorine is 50%, at 250 ℃ of lower oxidizing roasting 0.5h.
(4) roasting product in the described step (3) is dissolved, amount of water is 3 times of roasting product quality, and mixing speed is 10r/min, churning time is 10min, carry out solid-liquid separation, the gained solid phase mainly is unreacted Manganse Dioxide, and the gained liquid phase is potassium manganate solution; Among this embodiment in the pyrolusite transformation efficiency of manganese be 93.7%.
Claims (4)
1. method of producing potassium manganate or sodium manganate is characterized in that preparation process is as follows:
(1) take manganese carbonate ore or manganese oxide ore breeze as raw material, add potassium hydroxide or sodium hydroxide, put into stoving oven after fully stirring, at 300～850 ℃ of lower sintering 0.5～2h; Manganese carbonate ore or manganese oxide ore breeze and potassium hydroxide or sodium hydroxide manganese alkali mol ratio are 1:2～3.6; The content of manganese is 20%～63% in described manganese carbonate ore or the manganese oxide ore breeze; The granularity of described manganese carbonate ore or manganese oxide ore breeze accounts for more than 70% for-200 orders;
(2) be 70%～90% with levigate extremely-200 order content of described step (1) gained sintered material;
(3) pulverulent material that described step (2) is obtained adds gas-solid fluidized bed reactor, passes into oxidizing gas, regulates air flow and makes material be in fluidized state, keeps 220～300 ℃ of reactor temperatures, reaction 0.5～3h;
(4) potassium manganate that described step (3) is obtained or sodium manganate roasting product dissolve, stir and leave standstill 10～30min, carry out solid-liquid separation, and liquid phase is potassium manganate or sodium manganate solution, and solid phase mainly is unreacted manganese ore, return step (1) again; Amount of water is 2～5 times of roasting material during dissolving.
2. the method for described production potassium manganate or sodium manganate according to claim 1 is characterized in that described abundant stirring is first that potassium hydroxide or sodium hydroxide is water-soluble, manganese carbonate ore or manganese oxide ore breeze is added to carry out roasting after blending together mashed prod in the solution more again; Described potassium hydroxide or sodium hydroxide solution mass percent concentration are 35%～55%.
3. the method for described production potassium manganate or sodium manganate according to claim 1 is characterized in that described stoving oven is open hearth or rotary kiln.
4. the method for described production potassium manganate or sodium manganate according to claim 1 is characterized in that step (3) oxidizing gas is air, oxygen or chlorine, and water content is 20～300g/m in its Air and the oxygen
3, the volume fraction of nitrogen, air or oxygen is 0～90% in the chlorine.
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| CN103896339B (en) * | 2012-12-27 | 2016-08-24 | 北京汉能创昱科技有限公司 | A kind of preparation method of sodium manganese oxide |
| CN103172119B (en) * | 2013-04-17 | 2014-12-17 | 湖南化工研究院 | Preparation method of layered chemical manganese dioxide |
| CN109830671A (en) * | 2019-03-06 | 2019-05-31 | 四川大学 | A kind of tunnel recombination structure material and the sodium-ion battery positive material using tunnel recombination structure material preparation |
| CN112794367B (en) * | 2019-11-13 | 2021-11-09 | 中国科学院大连化学物理研究所 | Preparation method of potassium permanganate |
| CN110791668B (en) * | 2019-11-13 | 2022-11-11 | 兰州理工大学 | Method for recovering manganese from lithium ion battery anode waste containing manganese element |
| CN113683121A (en) * | 2021-09-13 | 2021-11-23 | 云南群星化工有限公司 | Process for preparing potassium manganate by solid-phase normal-pressure oxidation |
| CN114480874B (en) * | 2022-02-11 | 2023-09-26 | 长沙有色冶金设计研究院有限公司 | Method for removing manganese ions in high-manganese zinc concentrate leaching solution and application thereof |
| CN114408980A (en) * | 2022-02-11 | 2022-04-29 | 长沙有色冶金设计研究院有限公司 | Preparation method and equipment of demanganizing agent |
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| CN101367554B (en) * | 2008-09-24 | 2010-12-15 | 谭国华 | Method for preparing potassium manganate solution |
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