CN103570076A - Method for preparing potassium manganate - Google Patents
Method for preparing potassium manganate Download PDFInfo
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- CN103570076A CN103570076A CN201310594755.4A CN201310594755A CN103570076A CN 103570076 A CN103570076 A CN 103570076A CN 201310594755 A CN201310594755 A CN 201310594755A CN 103570076 A CN103570076 A CN 103570076A
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- potassium hydroxide
- hydroxide solution
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Abstract
The invention discloses a method for preparing potassium manganate. The method comprises the following steps: in an oxygen-enriched atmosphere, at 250-260 DEG C and 0.2-1.2 MPa, causing a first potassium hydroxide solution with concentration being 45-70 weight percent and manganese dioxide to conduct oxidation reaction to obtain potassium manganate material liquid; standing the potassium manganate material liquid and carrying out solid-liquid separation to respectively obtain supernatant and bottom flow; utilizing a second potassium hydroxide solution to adjust the baume degree of the bottom flow to 50 and then staying for crystal growing to obtain a first solid-liquid mixture; carrying out first filter-pressing separation for the first solid-liquid mixture to respectively a solid mixture and filter-pressing waste liquid, wherein the solid mixture is potassium manganate. The method utilized for producing potassium manganate has the advantages of simple production processes, high manganese dioxide conversion rate, high recovery rate of manganese and potassium hydroxide, low energy consumption, cleanness and environmental friendliness.
Description
Technical field
The present invention relates to chemical field, particularly, relate to the method for preparing potassium manganate.
Background technology
At present, industrial potassium permanganate technology of preparing is mainly divided into solid-phase oxidation method and liquid phase oxidation.Solid-phase oxidation method is due to restriction and the MnO of technique itself
2powder poor activity, MnO
2it is very incomplete that oxidizing reaction is carried out, and causes MnO
2low conversion rate.Still there is Manganse Dioxide low conversion rate, manganese, the KOH rate of recovery is low, energy consumption is high, environmental pollution is serious problem in the preparation section that liquid phase oxidation is prepared potassium manganate in potassium permanganate process.
Thereby preparation method and the equipment of potassium manganate still have much room for improvement at present.
Summary of the invention
The present invention is intended at least solve one of technical problem existing in prior art.For this reason, one object of the present invention be to propose a kind ofly have that production process is simple, Manganse Dioxide transformation efficiency is high, manganese and the potassium hydroxide rate of recovery is high, the method for preparing potassium manganate of energy-conserving and environment-protective.
In one aspect of the invention, the invention provides a kind of method of preparing potassium manganate.According to embodiments of the invention, the method comprises the following steps: in oxygen enrichment atmosphere, under 250-260 degree Celsius, 0.2-1.2Mpa, making concentration is that the first potassium hydroxide solution and the Manganse Dioxide of 45-70 % by weight carries out oxidizing reaction, to obtain potassium manganate feed liquid; Described potassium manganate feed liquid is standing and carry out solid-liquid separation, to obtain respectively supernatant liquor and underflow; Utilizing the second potassium hydroxide solution to carry out degree Beaume adjusting to described underflow, is to stop growing the grain after 50 to the degree Beaume of described underflow, to obtain the first solidliquid mixture; And it is separated that described the first solidliquid mixture is carried out to the first press filtration, to obtain respectively solid mixture and press filtration waste liquid, described solid mixture is potassium manganate.Contriver is surprised to find, and utilizes method of the present invention to produce potassium manganate, and production process is simple, Manganse Dioxide transformation efficiency is high, and the rate of recovery of manganese and potassium hydroxide is high, and energy consumption is low, clean environment firendly, and, utilize method of the present invention can utilize the pyrolusite of low taste to prepare high-quality potassium manganate.
According to embodiments of the invention, described the first potassium hydroxide solution utilizes the preparation of sheet alkali to obtain, and described Manganse Dioxide provides with the form of pyrolusite.
According to embodiments of the invention, further comprise, after described press filtration waste liquid evaporation is concentrated, mix with described supernatant liquor, and add sheet alkali in mixed solution, to obtain described the first potassium hydroxide solution.Thus, supernatant liquor recycle can be improved to the rate of recovery of potassium hydroxide, thereby reach the object that reduces reagent consumption, reduces costs.
According to embodiments of the invention, in described Manganse Dioxide and described the first potassium hydroxide solution, the mass ratio of potassium hydroxide is 1:5-15.Thus, be conducive to Manganse Dioxide and fully react, thus the transformation efficiency of raising Manganse Dioxide, and then the productive rate of raising potassium manganate.
According to embodiments of the invention, carry out described stop growing the grain at least 3 days.Thus, the potassium manganate crystalline structure of generation is stable is convenient to subsequent operations.
According to embodiments of the invention, further comprise: utilize the 3rd potassium hydroxide solution to adjust liquid to process to described potassium manganate, to obtain the second solidliquid mixture, in described the second solidliquid mixture, concentration of potassium hydroxide is 2-5 % by weight, and potassium manganate concentration is 120～150g/l; Described the second solidliquid mixture is carried out to the second press filtration separated, to obtain respectively potassium manganate solution and waste residue; Described potassium manganate solution is carried out to electrolysis and suction filtration successively, to obtain potassium permanganate coarse-grain and electrolysis mother liquor; And described potassium permanganate coarse-grain is carried out to complex crystallization and drying treatment successively, to obtain potassium permanganate crystals.Thus, can remove the impurity in potassium manganate coarse-grain, and can effectively utilize the potassium manganate after removal of impurities to prepare potassium permanganate.
According to embodiments of the invention, further comprise: described press filtration waste liquid evaporation is concentrated, and mix with described supernatant liquor, to obtain described the 3rd potassium hydroxide solution.Thus, can be by press filtration waste liquid and supernatant liquor recycle, thus improve the rate of recovery of potassium hydroxide, reduce the consumption of raw material, avoid waste liquid directly discharge and contaminate environment, and then reach and reduce costs, Jie Neng Jian Mao, the object of clean environment firendly.
According to embodiments of the invention, described the second potassium hydroxide solution provides with the form of electrolysis mother liquor.Thus, electrolysis mother liquor can be recycled, thereby reduce discharging of waste liquid, improve the rate of recovery of potassium hydroxide, reach and reduce production costs, the object of energy-conserving and environment-protective.
Compared with prior art, the method for preparing potassium manganate of the present invention, has the following advantages:
(1) utilize method of the present invention to prepare potassium manganate, Manganse Dioxide transformation efficiency is high, and the rate of recovery of manganese and potassium hydroxide is high;
(2) method of preparing potassium manganate of the present invention is utilized clean energy, and less to the pollution of environment, effects of energy conservation and environmental protection is more remarkable;
(3) method of the present invention more easily realizes industrial, to equipment without particular requirement, more easy operation control;
(4) method well-oxygenated environment of the present invention is stronger, can utilize low-grade pyrolusite to prepare high-quality potassium permanganate.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination obviously and is easily understood becoming the description of embodiment, wherein:
Fig. 1 has shown according to one embodiment of present invention, prepares the schematic flow sheet of the method for potassium manganate;
Fig. 2 has shown according to one embodiment of present invention, the structural representation of reactor;
Fig. 3 has shown according to another embodiment of the invention, the structural representation of reactor; And
Fig. 4 shown according to one embodiment of present invention, for the preparation of the structural representation of the system of potassium manganate.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Below by the embodiment being described with reference to the drawings, be exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, term " longitudinally ", " laterally ", " on ", orientation or the position relationship of the indication such as D score, 'fornt', 'back', " left side ", " right side ", " vertically ", " level ", " top ", " end " be based on orientation shown in the drawings or position relationship, be only the present invention for convenience of description rather than require the present invention with specific orientation structure and operation, therefore can not be interpreted as limitation of the present invention.
In the present invention, the terms such as unless otherwise clearly defined and limited, term " is connected ", " connection ", " fixing " should be interpreted broadly, and for example, can be to be fixedly connected with, and can be also to removably connect, or connect integratedly; Can be mechanical connection, can be to be also electrically connected to; Can be to be directly connected, also can indirectly be connected by intermediary, can be the connection of two element internals.For the ordinary skill in the art, can understand as the case may be above-mentioned term concrete meaning in the present invention.
It should be noted that, term " first ", " second " be only for describing object, and can not be interpreted as indication or hint relative importance or the implicit quantity that indicates indicated technical characterictic.Thus, one or more these features can be expressed or impliedly be comprised to the feature that is limited with " first ", " second ".
According to an aspect of the present invention, the present invention proposes a kind of method of preparing potassium manganate.According to embodiments of the invention, with reference to Fig. 1, the method comprises the following steps:
S100: in oxygen enrichment atmosphere, the first potassium hydroxide solution and Manganse Dioxide carry out oxidizing reaction, to obtain potassium manganate feed liquid
First, in oxygen enrichment atmosphere, make the first potassium hydroxide solution and Manganse Dioxide carry out oxidizing reaction, to obtain potassium manganate feed liquid.Wherein, the chemical reaction that this step relates generally to is: 2MnO
2+ 4KOH+O
2→ 2K
2mnO
4↓+2H
2o.
According to embodiments of the invention, the concentration of the condition of oxidizing reaction and the first potassium hydroxide solution is all not particularly limited.According to some embodiments of the present invention, can be in oxygen enrichment atmosphere, under 250-260 degree Celsius, 0.2-1.2Mpa condition, the first potassium hydroxide solution and the Manganse Dioxide that by concentration, are 45-70 % by weight carry out oxidizing reaction, to obtain potassium manganate feed liquid.Thus, can make potassium hydroxide and Manganse Dioxide, under optimal condition, oxidizing reaction occur, thereby can improve the transformation efficiency of Manganse Dioxide, and then improve the productive rate of potassium manganate.
According to embodiments of the invention, the source of described the first potassium hydroxide solution and Manganse Dioxide provides form to be not particularly limited, and in practical application, those skilled in the art can select as the case may be flexibly.According to some embodiments of the present invention, described the first potassium hydroxide solution utilizes the preparation of sheet alkali to obtain, particularly, described the first potassium hydroxide solution is to mix with supernatant liquor after press filtration waste liquid evaporation is concentrated, and obtains to adding sheet alkali in mixed solution; Described Manganse Dioxide provides with the form of pyrolusite.Thus, supernatant liquor recycle can be improved to the rate of recovery of potassium hydroxide, thereby reach the object that reduces reagent consumption, reduces costs.
According to embodiments of the invention, the proportioning of described Manganse Dioxide and described the first potassium hydroxide solution is not particularly limited.According to concrete examples more of the present invention, the ratio that is 1:5-15 according to mass ratio of potassium hydroxide in described Manganse Dioxide and described the first potassium hydroxide solution is carried out to oxidizing reaction.Thus, be conducive to Manganse Dioxide and fully react, thus the transformation efficiency of raising Manganse Dioxide, and then the productive rate of raising potassium manganate.
S200: described potassium manganate feed liquid is standing and carry out solid-liquid separation, to obtain respectively supernatant liquor and underflow
Then, by after the standing appropriate time of potassium manganate feed liquid obtaining in S100 step, carry out solid midnight from, to obtain respectively supernatant liquor and underflow.In the separated supernatant liquor obtaining, contain potassium hydroxide, can be further used for configuring the first potassium hydroxide solution and the 3rd potassium hydroxide solution, thereby realize the recycle of potassium hydroxide, and then reduce reagent consumption and discharging of waste liquid, reduce costs clean environment firendly.Main component in the separated underflow obtaining is potassium manganate, treats subsequent step processing.
S300: utilize the second potassium hydroxide solution to carry out stopping growing the grain after degree Beaume adjusting to underflow, to obtain the first solidliquid mixture
Next, utilizing the second potassium hydroxide solution to carry out degree Beaume adjusting to described underflow, is to stop growing the grain after 50 to the degree Beaume of described underflow, to obtain the first solidliquid mixture.Contriver is surprised to find, and when the degree Beaume of underflow is adjusted to 50, the amount that the potassium manganate crystal disproportionation reaction of generation generates Manganse Dioxide is few, and the rate of recovery of potassium manganate is high, and the degree Beaume of described underflow is too high or too low all can not reach best effect.
According to embodiments of the invention, the presentation mode of described the second potassium hydroxide solution is not particularly limited.According to concrete examples more of the present invention, described the second potassium hydroxide solution provides with the form of electrolysis mother liquor.Thus, can recycle electrolysis mother liquor, improve the rate of recovery of potassium hydroxide, thereby reach minimizing raw material consumption, reduce production costs, reduce discharging of waste liquid, the object of protection of the environment.
According to embodiments of the invention, the time that stops growing the grain is not particularly limited, and those skilled in the art can select flexibly according to practical situation.According to concrete examples more of the present invention, carry out described stop growing the grain at least 3 days.Thus, the potassium manganate crystalline structure of generation is stable, is convenient to subsequent operations.
S400: described the first solidliquid mixture is carried out to the first press filtration separated, to obtain respectively solid mixture and press filtration waste liquid
Next, the first solidliquid mixture obtaining in step S300 is carried out to press filtration separation, to obtain solid mixture and press filtration waste liquid.The separated solid mixture obtaining is potassium manganate.In the separated press filtration waste liquid obtaining, contain a certain amount of potassium hydroxide, further recycle.According to some embodiments of the present invention, after press filtration waste liquid evaporation can being concentrated, mix with supernatant liquor, and add sheet alkali, prepare the first potassium hydroxide solution.According to other embodiment of the present invention, after press filtration waste liquid evaporation can being concentrated, mix with supernatant liquor, prepare the 3rd potassium hydroxide solution.Thus, realize the recycling of press filtration waste liquid, thereby improved the rate of recovery of potassium hydroxide, reduced discharging of waste liquid, reached Jie Neng Jian Mao, the object of clean environment firendly.
The potassium manganate that above-mentioned steps prepares can be through being further used for preparing potassium permanganate.Therefore,, according to some embodiments of the present invention, the method for preparing potassium manganate of the present invention is further comprising the steps:
Utilize the 3rd potassium hydroxide solution to adjust liquid to process to potassium manganate, to obtain the second solidliquid mixture
Due in oxidation reaction process, can there is side reaction SiO
2+ 2KOH=K
2siO
3+ H
2o, thereby, in the potassium manganate crystal preparing through abovementioned steps, also contain a small amount of K
2siO
3impurity, in order to obtain the potassium manganate that purity is higher, can utilize the 3rd potassium hydroxide solution to adjust liquid to process to described potassium manganate, to obtain the second solidliquid mixture.After toning liquid, described potassium manganate dissolution of crystals is in liquid phase, and potassium silicate impurity does not dissolve, and stays in solid phase, thus, further passes through solid-liquid separation, can effectively remove the potassium silicate impurity in potassium manganate.In addition, because potassium silicate has stronger absorption property, other impurity can be further adsorbed on the surface of solid silicic acid potassium, thereby can further purify potassium manganate, and then obtains the higher potassium manganate solution of purity.
The second solidliquid mixture is carried out to the second press filtration separated, to obtain respectively potassium manganate solution and waste residue
Then, the second solidliquid mixture is carried out to press filtration separation, to obtain potassium manganate solution and waste residue.Thus, can efficiently the solid impurity in the second solidliquid mixture be removed, obtain the higher potassium manganate solution of purity, thereby be conducive to the carrying out of subsequent step, raise the efficiency.
Potassium manganate solution is carried out to electrolysis and suction filtration successively, to obtain potassium permanganate coarse-grain and electrolysis mother liquor
Next, first the potassium manganate solution of above-mentioned acquisition is carried out to electrolysis, to make potassium manganate reaction generate potassium permanganate.Wherein, the chemical reaction that this step relates generally to is: K
2mnO
4+ H
2o=KMnO
4+ 1/2H
2+ KOH.
Subsequently, the solution after electrolysis is carried out to suction filtration, to obtain potassium permanganate coarse-grain and electrolysis mother liquor.By above-mentioned reaction equation, can be found out, in described electrolysis mother liquor, contain a certain amount of potassium hydroxide, thereby can carry out recycling to it.According to some embodiments of the present invention, can, using electrolysis mother liquor directly as the second potassium hydroxide solution, to described underflow, carry out degree Beaume adjusting.Thus, realize the recycle of electrolysis mother liquor, thereby reached raising raw material availability, reduced discharging of waste liquid, reduced costs the object of protection of the environment.
Potassium permanganate coarse-grain is carried out to complex crystallization and drying treatment successively, to obtain potassium permanganate crystals
Because the content of potassium permanganate in the potassium permanganate coarse-grain preparing is lower, thereby need to carry out complex crystallization processing to potassium permanganate coarse-grain, to improve the content of potassium permanganate.Particularly, potassium permanganate coarse-grain is dissolved in deionized water, then makes the potassium permanganate crystallization again in solution, thereby obtain the potassium permanganate crystals that crystal grain is larger, potassium permanganate content is higher.
Above part has been described the method for preparing potassium manganate of the present invention in detail, in order to understand better the method, is described in detail below to implementing the equipment of the method again.
According to a further aspect in the invention, the present invention also provides a kind of reactor 1000.According to embodiments of the invention, with reference to Fig. 2 and Fig. 3, described reactor 1000 comprises: body 100, ore pulp heating unit 200 and whipping appts 300.Contriver is surprised to find, and utilizes reactor 1000 of the present invention, can prepare efficiently potassium manganate, and this structure of reactor is simple, easy to operate, uses clean energy, and heat utilization efficiency is high, is easy to realize large-scale industrialization and produces.
According to embodiments of the invention, in described body 100, be limited with reaction compartment, described body 100 tops are arranged at intervals with oxygen intake 101, useless oxygen outlet 102 and opening for feed 103, described body 100 middle and upper parts are provided with discharge port 104, described oxygen intake 101 is for to described reaction compartment delivering oxygen or oxygen-rich air, described useless oxygen outlet 102 is for discharging remaining oxygen and the water vapour in described reaction compartment, described opening for feed 103 is for transfer ore pulp in described reaction compartment, described discharge port 104 carries out for the described ore pulp of discharging in described reaction compartment the potassium manganate feed liquid obtaining after oxidizing reaction.
According to embodiments of the invention, described reactor 1000 has a plurality of oxygen intakes 101.Thus, can be quick, a large amount of by oxygen or oxygen-rich air is transported in reaction compartment and it is uniformly distributed in reaction compartment, guarantee stronger well-oxygenated environment in reaction compartment, thereby improve the efficiency of oxidizing reaction.
According to embodiments of the invention, the first potassium hydroxide solution and Manganse Dioxide that described ore pulp is 45-70 % by weight by concentration are mixed.Thus, be conducive to Manganse Dioxide and fully react, improve the transformation efficiency of Manganse Dioxide, thereby efficiently prepare potassium manganate.
According to embodiments of the invention, the source of described the first potassium hydroxide solution and described Manganse Dioxide provides form to be not particularly limited.According to some embodiments of the present invention, described the first potassium hydroxide solution utilizes the preparation of sheet alkali to obtain, and described Manganse Dioxide provides with the form of pyrolusite.According to concrete examples more of the present invention, described the first potassium hydroxide solution is by mixing with described supernatant liquor after described press filtration waste liquid evaporation is concentrated and add the acquisition of sheet alkali in mixed solution.Thus, supernatant liquor recycle can be improved to the rate of recovery of potassium hydroxide, thereby reach the object that reduces reagent consumption, reduces costs.
According to embodiments of the invention, the ratio of described Manganse Dioxide and described the first potassium hydroxide solution is not particularly limited.According to some embodiments of the present invention, in described ore pulp, the mass ratio of described Manganse Dioxide and described potassium hydroxide is 1:5-15.Thus, be conducive to Manganse Dioxide and fully react, thus the transformation efficiency of raising Manganse Dioxide, and then the productive rate of raising potassium manganate.
According to embodiments of the invention, the pressure in described reactor 1000 is not particularly limited.According to concrete examples more of the present invention, described reactor 1000 internal pressures are 0.2-1.2Mpa.Thus, can under optimal pressure condition, react, be conducive to improve reaction efficiency.
According to embodiments of the invention, described ore pulp heating unit 200 is arranged in described body 100, for described ore pulp is heated to 250-260 degree Celsius.According to embodiments of the invention, described ore pulp heating unit 200 is far infrared heater.Thus, can effectively utilize clean energy to heat reaction raw materials, less to the pollution of environment, effects of energy conservation and environmental protection be more remarkable, and heat utilization efficiency is higher.
According to embodiments of the invention, described whipping appts 300 is arranged at described body 100 inside, for described ore pulp is stirred.According to some embodiments of the present invention, described whipping appts 300 comprises stirring arm and is located on described stirring arm and along a plurality of blades that are axially spaced apart from each other of described stirring arm.Thus, be conducive to described flowsheet of slurry agitation even.According to other embodiment of the present invention, the material of described stirring rake and paddle is not particularly limited.According to concrete examples more of the present invention, described stirring rake is made by 718 alloys, and described blade is made by Martensite Stainless Steel.Thus, stirring rake and paddle have good alkali corrosion resistance and oxygen corrosion performance, thereby can extend its work-ing life.
According to embodiments of the invention, the type of described reactor 1000 is not particularly limited.According to some embodiments of the present invention, described reactor is vertical response still (Fig. 2), and when described reactor 1000 is vertical response still, described discharge port 104 is arranged at described body 100 lower sidewall.According to other embodiment of the present invention, described reactor 1000 is horizontal reacting still (Fig. 3), when described reactor 1000 is horizontal reacting still, described discharge port 104 is arranged at described body 100 tops, and arranges with described oxygen intake 101, described useless oxygen outlet 102 and described opening for feed 103 intervals.
According to embodiments of the invention, with reference to Fig. 2 and Fig. 3, described reactor 1000 further comprises: oxygen heating arrangement 400, described oxygen heating arrangement 400 is communicated with described oxygen intake 101, before oxygen or oxygen-rich air carrying to described reaction compartment, described oxygen or oxygen-rich air are preheated to 200 degrees Celsius.Thus, utilize oxygen heating arrangement 400, can effectively oxygen or oxygen-rich air be preheated to the required temperature of oxidizing reaction, thereby be conducive to the carrying out of oxidizing reaction, and then improve efficiency.
According to embodiments of the invention, with reference to Fig. 2 and Fig. 3, described reactor 1000 further comprises: minute device of air 500, within described minute, device of air 500 is connected with described a plurality of oxygen intakes 101 with described oxygen heating arrangement 400 respectively, for oxygen or oxygen-rich air through described oxygen heating arrangement 400 preheatings are dispensed to each oxygen intake 101.Thus, can efficiently oxygen or oxygen-rich air be transported in reaction compartment, maintain well-oxygenated environment stronger in reaction compartment, thereby improve reaction efficiency.
According to embodiments of the invention, with reference to Fig. 2 and Fig. 3, described reactor 1000 further comprises: gas-liquid separator 600, described gas-liquid separator 600 has import, venting port and water port, described import is connected with described useless oxygen outlet 102, described venting port is for discharging the oxygen after separation, described water port is connected with described reaction compartment, described gas-liquid separator is for carrying out gas-liquid separation by described remaining oxygen and the water vapour of discharging from described useless oxygen outlet, and the oxygen after separation is discharged to described gas-liquid separator and the liquid after separation is flowed to described reaction compartment.Thus, the water that can be effectively useless oxygen be carried and a small amount of potassium hydroxide reclaim, so can water saving, improve the rate of recovery of potassium hydroxide.
According to embodiments of the invention, described reactor 1000 further comprises oxygen hose (not shown), described oxygen hose is along the described body of being axially set in of described body 100 100 inside, and be communicated with described oxygen intake 101, for by the oxygen delivery entering from described oxygen intake 101 to described reaction compartment bottom.Thus, be conducive to ore pulp and fully contact with oxygen, thereby improve reaction efficiency.According to embodiments of the invention, the material of described oxygen hose is not particularly limited.According to concrete examples more of the present invention, described oxygen hose is made by Martensite Stainless Steel.Thus, described oxygen hose has good alkali corrosion resistance and oxygen corrosion performance, and work-ing life is longer.
In accordance with a further aspect of the present invention, the present invention also provides a kind of system for the preparation of potassium manganate.According to embodiments of the invention, with reference to Fig. 4, the system for the preparation of potassium manganate of the present invention comprises: foregoing reactor 1000, equipment for separating liquid from solid 2000, stops rystallization device 3000, and the first press filtration tripping device 4000.According to embodiments of the invention, described reactor 1000 is in oxygen enrichment atmosphere, and under 250-260 degree Celsius, 0.2-1.2Mpa, making concentration is that the first potassium hydroxide solution and the Manganse Dioxide of 60-75 % by weight carries out oxidizing reaction, to obtain potassium manganate feed liquid; Described equipment for separating liquid from solid 2000 is connected with described reactor 1000, for receiving potassium manganate feed liquids from described reactor 1000, and described potassium manganate feed liquid is standing and carry out solid-liquid separation, to obtain respectively supernatant liquor and underflow; Described stop rystallization device 3000 is connected with described equipment for separating liquid from solid 2000, for receiving described underflow from described equipment for separating liquid from solid 2000, and utilize the second potassium hydroxide solution to carry out degree Beaume adjusting to described underflow, to the degree Beaume of described underflow, be to stop growing the grain after 50, to obtain the first solidliquid mixture; Described the first press filtration tripping device 4000 is connected with described stop rystallization device 3000, for receiving described the first solidliquid mixture from described stop rystallization device 3000 and carrying out the first press filtration separation, to obtain respectively solid mixture and press filtration waste liquid, described solid mixture is described potassium manganate.Contriver is surprised to find, utilize the system of preparing potassium manganate of the present invention, can effectively implement the method for preparing potassium manganate of the present invention, and the technique that this system relates to is simple, safety, and the transformation efficiency of Manganse Dioxide is high, the rate of recovery of manganese and potassium hydroxide is high, heat utilization efficiency is high, energy consumption is low, clean environment firendly.
According to embodiments of the invention, described in stop growing the grain time be not particularly limited.According to concrete examples more of the present invention, carry out described stop growing the grain at least 3 days.Thus, the potassium manganate crystalline structure of generation is stable is convenient to subsequent operations.
According to embodiments of the invention, the described system of preparing potassium manganate further comprises dosing unit (not shown), described dosing unit is connected with described reactor 1000, be used for preparing described the first potassium hydroxide solution and add Manganse Dioxide to prepare ore pulp to described the first potassium hydroxide solution, and by described pulp conveying to described reactor 1000.
According to embodiments of the invention, the described system of preparing potassium manganate further comprises supernatant liquor transfer lime (not shown), described supernatant liquor transfer lime is connected with described dosing unit with described equipment for separating liquid from solid 2000 respectively, for described supernatant liquor being delivered to described dosing unit to prepare described the first potassium hydroxide solution.
According to embodiments of the invention, the described system of preparing potassium manganate further comprises: adjust liquid processing device (not shown), the second press filtration tripping device (not shown), electrolyzer (not shown), suction filtration device (not shown), and complex crystallization device (not shown).According to embodiments of the invention, described tune liquid processing device is connected with described the first press filtration tripping device 4000, for receiving described potassium manganate from described the first press filtration tripping device 4000, utilize the 3rd potassium hydroxide solution to adjust liquid to process to obtain the second solidliquid mixture to described potassium manganate, in described the second solidliquid mixture, concentration of potassium hydroxide is 2-5 % by weight, and potassium manganate concentration is 120～150g/l; Described the second press filtration tripping device is connected with described tune liquid processing device, separated for receiving described the second solidliquid mixture from described tune liquid processing device and carrying out the second press filtration, to obtain respectively potassium manganate solution and waste residue; Described electrolyzer is connected with described the second press filtration tripping device, for receiving described potassium manganate solution from described the second press filtration tripping device, and described potassium manganate solution is carried out to electrolysis, to obtain potassium permanganate feed liquid; Described suction filtration device is connected with described electrolyzer, for receive described potassium permanganate feed liquid from described electrolyzer, and described potassium permanganate feed liquid is carried out to suction filtration processing, to obtain potassium permanganate coarse-grain and electrolysis mother liquor; Described complex crystallization device is connected with described suction filtration device, for receiving described potassium permanganate coarse-grain from described suction filtration device, and described potassium permanganate coarse-grain is carried out to complex crystallization and drying treatment successively, to obtain potassium permanganate crystals.Thus, can remove the impurity in potassium manganate coarse-grain, and can effectively utilize the potassium manganate after removal of impurities to prepare potassium permanganate.
According to embodiments of the invention, further comprise electrolysis mother liquor transfer lime (not shown), described electrolysis mother liquor transfer lime is connected with described stop rystallization device with described suction filtration device respectively, for described electrolysis mother liquor is delivered to described stop rystallization device, usings, as described the second potassium hydroxide solution, described underflow is carried out to degree Beaume adjusting.Thus, can be by the recycling of electrolysis mother liquor, thereby reduce reagent consumption, reduce production costs, reduce discharging of waste liquid, protection of the environment.
According to embodiments of the invention, described the 3rd potassium hydroxide solution mixes acquisition with described supernatant liquor after described press filtration waste liquid evaporation is concentrated.Thus, can be by press filtration waste liquid and supernatant liquor recycle, thus improve the rate of recovery of potassium hydroxide, reduce the consumption of raw material, avoid waste liquid directly discharge and contaminate environment, and then reach and reduce costs, Jie Neng Jian Mao, the object of clean environment firendly.
Below with reference to Fig. 2-4, further reactor of the present invention and system under working order are described:
First, press filtration waste liquid after supernatant liquor and evaporation concentration is transported to dosing unit through supernatant liquor transfer lime and press filtration waste liquid transfer lime respectively, sheet alkali in dosing unit and pyrolusite mix with the press filtration waste liquid after supernatant liquor and evaporation concentration, obtain ore pulp, then ore pulp is transported in the reaction compartment of reactor 1000 by opening for feed 103, oxygen is preheating to 200 degrees Celsius through oxygen heating arrangement 400(successively simultaneously), divide device of air 500, by oxygen intake 101, be passed in reaction compartment, under the condition that whipping appts 300 stirs and heating unit 200 heats, in reaction compartment, there is oxidizing reaction in ore pulp and oxygen, obtain potassium manganate feed liquid, in reaction process, useless oxygen is transported to gas-liquid separator 600 by useless oxygen outlet 102, useless oxygen after gas-liquid separation is emptying, liquid is returned to reaction compartment, next potassium manganate feed liquid is transported to equipment for separating liquid from solid 2000 through discharge port 104, in equipment for separating liquid from solid 2000, carry out solid-liquid separation, obtain supernatant liquor and underflow, supernatant liquor is from flowing into supernatant liquor storage tank (not shown) and being delivered to dosing unit for batching through supernatant liquor transfer lime, underflow is transported to and stops rystallization device 3000, by the second potassium hydroxide solution, regulated after degree Beaume to 50, in stopping rystallization device 3000, stop growing the grain, obtain the first solidliquid mixture, the first solidliquid mixture is transported to the first filter-pressing device 4000 and carries out press filtration separation subsequently, the separated press filtration waste liquid obtaining is transported to press filtration waste liquid storage tank (not shown) and is delivered to dosing unit for batching through press filtration waste liquid transfer lime, the separated potassium manganate coarse-grain obtaining is transported to adjusts liquid processing device (not shown), after the 3rd potassium hydroxide solution adjusts liquid to process, the second solidliquid mixture obtaining is transported to the second press filtration tripping device (not shown) and carries out press filtration separation, the separated filtrate obtaining is transported to electrolyzer (not shown), potassium manganate is generated potassium permanganate by electrolysis in electrolyzer, obtain potassium permanganate feed liquid, then potassium permanganate feed liquid is transported to suction filtration device (not shown) and carries out suction filtration, the electrolysis mother liquor that suction filtration obtains is transported to electrolysis mother liquor storage tank (not shown) and is delivered to tune liquid processing device through pipeline, the potassium permanganate coarse-grain obtaining is transported to complex crystallization device (not shown) and carries out complex crystallization and drying treatment, obtain thus potassium permanganate crystals.
Embodiment 1
Utilize the reactor shown in Fig. 2 or Fig. 3, and the system shown in Fig. 4, according to the foregoing method of preparing potassium manganate, prepare in accordance with the following steps potassium manganate:
A. oxidizing reaction: concentration is that the ratio that the first potassium hydroxide solution of 45-70 % by weight is 1:5-15 with pyrolusite according to the potassium hydroxide mass ratio mixing in Manganse Dioxide and the first potassium hydroxide solution is mixed to form ore pulp, in oxygen enrichment atmosphere, under 250-260 degree Celsius, 0.2-1.2Mpa condition, carry out oxidizing reaction, to obtain potassium manganate feed liquid;
B. admittedly midnight from: after the standing appropriate time of potassium manganate feed liquid, carry out solid-liquid separation, to obtain respectively supernatant liquor and underflow;
C. stop growing the grain: utilize the second potassium hydroxide solution to carry out degree Beaume adjusting to underflow, after being 50 to the degree Beaume of underflow, stop growing the grain at least 3 days, to obtain the first solidliquid mixture;
D. the first press filtration is separated: the first solidliquid mixture obtaining in step c is carried out to press filtration separation, the separated press filtration waste liquid obtaining is delivered to press filtration waste liquid storage tank, after evaporation concentration, for preparing the first potassium hydroxide solution and the 3rd potassium hydroxide solution, the separated solid obtaining is potassium manganate coarse-grain;
E. adjust liquid to process: to utilize the 3rd potassium hydroxide solution to adjust liquid to process to the potassium manganate coarse-grain obtaining in steps d, to obtain the second solidliquid mixture;
F. the second press filtration is separated: the second solidliquid mixture obtaining in step e is carried out to press filtration separation, to obtain potassium manganate solution and waste residue;
G. electrolysis: in electrolyzer, the potassium manganate solution obtaining in step f is carried out to electrolysis, potassium manganate is generated potassium permanganate by electrolysis, to obtain potassium permanganate feed liquid;
H. suction filtration: in suction filtration device, the potassium permanganate feed liquid obtaining in step g is carried out to suction filtration processing, to obtain potassium permanganate coarse-grain and electrolysis mother liquor, wherein electrolysis mother liquor is carried electrolysis mother liquor storage tank to be used for preparing the second potassium hydroxide solution, the solid of acquisition is potassium permanganate coarse-grain;
I. complex crystallization is with dry: in complex crystallization device, the potassium permanganate crystals obtaining in step h, by multiple water-soluble, is carried out complex crystallization, further to carrying out drying treatment through complex crystallization acquisition potassium permanganate crystals, thereby obtains industrial potassium permanganate.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that not departing from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (8)
1. a method of preparing potassium manganate, is characterized in that, comprises the following steps:
In oxygen enrichment atmosphere, under 250-260 degree Celsius, 0.2-1.2Mpa, making concentration is that the first potassium hydroxide solution and the Manganse Dioxide of 45-70 % by weight carries out oxidizing reaction, to obtain potassium manganate feed liquid;
Described potassium manganate feed liquid is standing and carry out solid-liquid separation, to obtain respectively supernatant liquor and underflow;
Utilizing the second potassium hydroxide solution to carry out degree Beaume adjusting to described underflow, is to stop growing the grain after 50 to the degree Beaume of described underflow, to obtain the first solidliquid mixture; And
Described the first solidliquid mixture is carried out to the first press filtration separated, to obtain respectively solid mixture and press filtration waste liquid, described solid mixture is described potassium manganate.
2. method according to claim 1, is characterized in that, described the first potassium hydroxide solution utilizes the preparation of sheet alkali to obtain, and described Manganse Dioxide provides with the form of pyrolusite.
3. method according to claim 2, is characterized in that, further comprises:
After described press filtration waste liquid evaporation is concentrated, mix with described supernatant liquor, and add sheet alkali in mixed solution, to obtain described the first potassium hydroxide solution.
4. method according to claim 1, is characterized in that, in described Manganse Dioxide and described the first potassium hydroxide solution, the mass ratio of potassium hydroxide is 1:5-15.
5. method according to claim 1, is characterized in that, carries out described stop growing the grain at least 3 days.
6. method according to claim 1, is characterized in that, further comprises:
Utilize the 3rd potassium hydroxide solution to adjust liquid to process to described potassium manganate, to obtain the second solidliquid mixture, in described the second solidliquid mixture, concentration of potassium hydroxide is 2-5 % by weight, and potassium manganate concentration is 120～150g/l;
Described the second solidliquid mixture is carried out to the second press filtration separated, to obtain respectively potassium manganate solution and waste residue;
Described potassium manganate solution is carried out to electrolysis and suction filtration successively, to obtain potassium permanganate coarse-grain and electrolysis mother liquor; And
Described potassium permanganate coarse-grain is carried out to complex crystallization and drying treatment successively, to obtain potassium permanganate crystals.
7. method according to claim 6, is characterized in that, further comprises:
Described press filtration waste liquid evaporation is concentrated, and mix with described supernatant liquor, to obtain described the 3rd potassium hydroxide solution.
8. method according to claim 6, is characterized in that, described the second potassium hydroxide solution provides with the form of electrolysis mother liquor.
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| CN116040684A (en) * | 2023-02-22 | 2023-05-02 | 贵州大学 | Method for preparing potassium manganate by using pyrolusite |
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