CN103570076B - Prepare the method for potassium manganate - Google Patents
Prepare the method for potassium manganate Download PDFInfo
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- CN103570076B CN103570076B CN201310594755.4A CN201310594755A CN103570076B CN 103570076 B CN103570076 B CN 103570076B CN 201310594755 A CN201310594755 A CN 201310594755A CN 103570076 B CN103570076 B CN 103570076B
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Abstract
The invention discloses a kind of method preparing potassium manganate, the method is included in oxygen enrichment atmosphere, 250-260 degree Celsius, under 0.2-1.2Mpa, make concentration be that first potassium hydroxide solution of 45-70 % by weight and Manganse Dioxide carry out oxidizing reaction, to obtain potassium manganate feed liquid; Described potassium manganate feed liquid is left standstill and carries out solid-liquid separation, to obtain supernatant liquor and underflow respectively; Utilizing the second potassium hydroxide solution to carry out degree Beaume adjustment to described underflow, is carry out stop growing the grain, to obtain the first solidliquid mixture after 50 to the degree Beaume of described underflow; And described first solidliquid mixture is carried out the first press filtration separation, to obtain solid mixture and press filtration waste liquid respectively, described solid mixture is described potassium manganate.Utilize method of the present invention to produce potassium manganate, production process is simple, and manganese peroxide conversion rate is high, and the rate of recovery of manganese and potassium hydroxide is high, and energy consumption is low, clean environment firendly.
Description
Technical field
The present invention relates to chemical field, particularly, relate to the method 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 the restriction of technique itself and MnO
2powder poor activity, MnO
2it is very incomplete that oxidizing reaction is carried out, and causes MnO
2low conversion rate.The preparation section that liquid phase oxidation prepares potassium manganate in potassium permanganate process still exists that manganese peroxide conversion rate is low, manganese, the KOH rate of recovery is low, energy consumption is high, environmental pollution is serious problem.
Thus, the preparation method of current potassium manganate and equipment still have much room for improvement.
Summary of the invention
The present invention is intended at least to solve one of technical problem existed in prior art.For this reason, one object of the present invention be to propose a kind ofly have that production process is simple, manganese peroxide conversion rate is high, manganese and the potassium hydroxide rate of recovery is high, the method preparing potassium manganate of energy-conserving and environment-protective.
In one aspect of the invention, the invention provides a kind of method preparing potassium manganate.According to embodiments of the invention, the method comprises the following steps: in oxygen enrichment atmosphere, 250-260 degree Celsius, under 0.2-1.2Mpa, make concentration be that first potassium hydroxide solution of 45-70 % by weight and Manganse Dioxide carry out oxidizing reaction, to obtain potassium manganate feed liquid; Described potassium manganate feed liquid is left standstill and carries out solid-liquid separation, to obtain supernatant liquor and underflow respectively; Utilizing the second potassium hydroxide solution to carry out degree Beaume adjustment to described underflow, is carry out stop growing the grain, to obtain the first solidliquid mixture after 50 to the degree Beaume of described underflow; And described first solidliquid mixture is carried out the first press filtration separation, to obtain solid mixture and press filtration waste liquid respectively, described solid mixture is potassium manganate.Contriver is surprised to find, and utilize method of the present invention to produce potassium manganate, production process is simple, manganese peroxide conversion rate is high, and the rate of recovery of manganese and potassium hydroxide is high, and energy consumption is low, clean environment firendly, further, utilize method of the present invention that the pyrolusite of low taste can be utilized to prepare high-quality potassium manganate.
According to embodiments of the invention, described first potassium hydroxide solution utilizes sheet alkali to prepare and obtains, and described Manganse Dioxide provides with the form of pyrolusite.
According to embodiments of the invention, comprise further, mix with described supernatant liquor after described press filtration waste liquid evaporation is concentrated, and in mixed solution, add sheet alkali, to obtain described first potassium hydroxide solution.Thereby, it is possible to by supernatant liquor recycle, improve the rate of recovery of potassium hydroxide, thus reach the object reducing reagent consumption, reduce costs.
According to embodiments of the invention, in described Manganse Dioxide and described first potassium hydroxide solution, the mass ratio of potassium hydroxide is 1:5-15.Thus, be conducive to Manganse Dioxide and fully react, thus improve the transformation efficiency of Manganse Dioxide, and then improve the productive rate of 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, comprise further: utilize the 3rd potassium hydroxide solution to carry out the process of tune liquid to described potassium manganate, to obtain the second solidliquid mixture, in described second solidliquid mixture, concentration of potassium hydroxide is 2-5 % by weight, and potassium manganate concentration is 120 ~ 150g/l; Described second solidliquid mixture is carried out the second press filtration separation, to obtain potassium manganate solution and waste residue respectively; Described potassium manganate solution is carried out electrolysis and suction filtration successively, to obtain potassium permanganate coarse-grain and electrolysis mother liquor; And described potassium permanganate coarse-grain is carried out complex crystallization and drying treatment, successively to obtain potassium permanganate crystals.Thus, the impurity in potassium manganate coarse-grain can be removed, and the potassium manganate after can effectively utilizing removal of impurities prepares potassium permanganate.
According to embodiments of the invention, comprise further: described press filtration waste liquid evaporation is concentrated, and mixes with described supernatant liquor, to obtain described 3rd potassium hydroxide solution.Thus, can 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 to 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 second potassium hydroxide solution provides with the form of electrolysis mother liquor.Thereby, it is possible to utilized by electrolysis disposing mother liquor, thus reduce discharging of waste liquid, improve the rate of recovery of potassium hydroxide, reach reduction production cost, the object of energy-conserving and environment-protective.
Compared with prior art, the method preparing potassium manganate of the present invention, has the following advantages:
(1) utilize method of the present invention to prepare potassium manganate, manganese peroxide conversion rate is high, and the rate of recovery of manganese and potassium hydroxide is high;
(2) method preparing potassium manganate of the present invention utilizes 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 industrially more easily realizes, to equipment without particular requirement, and more easy operation control;
(4) method well-oxygenated environment of the present invention is stronger, and low-grade pyrolusite can be utilized to prepare the potassium permanganate of high-quality.
Additional aspect of the present invention and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 shows according to one embodiment of present invention, prepares the schematic flow sheet of the method for potassium manganate;
Fig. 2 shows according to one embodiment of present invention, the structural representation of reactor;
Fig. 3 shows according to another embodiment of the invention, the structural representation of reactor; And
Fig. 4 shows according to one embodiment of present invention, for the preparation of the structural representation of the system of potassium manganate.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Being exemplary below by the embodiment be described with reference to the drawings, only for explaining the present invention, and can not limitation of the present invention being interpreted as.
In describing the invention, term " longitudinal direction ", " transverse direction ", " on ", D score, "front", "rear", "left", "right", " vertically ", " level ", " top ", the orientation of the instruction such as " end " or position relationship be based on orientation shown in the drawings or position relationship, be only the present invention for convenience of description instead of require that the present invention with specific azimuth configuration and operation, therefore must can not be interpreted as limitation of the present invention.
In the present invention, unless otherwise clearly defined and limited, term " is connected ", " connection ", the term such as " fixing " should be interpreted broadly, and such as, can be fixedly connected with, also can be removably connect, or connect integratedly; Can be mechanical connection, also can be electrical connection; Can be directly be connected, also indirectly can be connected by intermediary, can be the connection of two element internals.For the ordinary skill in the art, above-mentioned term concrete meaning in the present invention can be understood as the case may be.
It should be noted that, term " first ", " second " only for describing object, and can not be interpreted as instruction or hint relative importance or imply the quantity indicating indicated technical characteristic.Thus, be limited with " first ", the feature of " second " can express or impliedly comprise one or more these features.
According to an aspect of the present invention, the present invention proposes a kind of method 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 condition of oxidizing reaction and the concentration of the first potassium hydroxide solution are all not particularly limited.According to some embodiments of the present invention, can in oxygen enrichment atmosphere, 250-260 degree Celsius, under 0.2-1.2Mpa condition, be 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 by concentration.Thereby, it is possible to make potassium hydroxide and Manganse Dioxide, under optimal condition, oxidizing reaction occur, thus the transformation efficiency of Manganse Dioxide can be improved, and then improve the productive rate of potassium manganate.
According to embodiments of the invention, namely the source of described 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 first potassium hydroxide solution utilizes sheet alkali to prepare and obtains, particularly, described first potassium hydroxide solution mixes with supernatant liquor after press filtration waste liquid evaporation is concentrated, and in mixed solution, add sheet alkali obtain; Described Manganse Dioxide provides with the form of pyrolusite.Thereby, it is possible to by supernatant liquor recycle, improve the rate of recovery of potassium hydroxide, thus reach the object reducing reagent consumption, reduce costs.
According to embodiments of the invention, the proportioning of described Manganse Dioxide and described first potassium hydroxide solution is not particularly limited.According to concrete examples more of the present invention, potassium hydroxide in described Manganse Dioxide and described first potassium hydroxide solution is 1:5-15 according to mass ratio ratio carries out oxidizing reaction.Thus, be conducive to Manganse Dioxide and fully react, thus improve the transformation efficiency of Manganse Dioxide, and then improve the productive rate of potassium manganate.
S200: described potassium manganate feed liquid left standstill and carry out solid-liquid separation, to obtain supernatant liquor and underflow respectively
Then, after the potassium manganate feed liquid obtained in S100 step is left standstill appropriate time, carry out solid midnight from, to obtain supernatant liquor and underflow respectively.Be separated in the supernatant liquor obtained and contain potassium hydroxide, configuration first potassium hydroxide solution and the 3rd potassium hydroxide solution can be further used for, thus achieve the recycle of potassium hydroxide, and then reduce reagent consumption and discharging of waste liquid, reduce costs, clean environment firendly.The main component be separated in the underflow obtained is potassium manganate, treats subsequent step process.
S300: carry out stop growing the grain, to obtain the first solidliquid mixture after utilizing the second potassium hydroxide solution to carry out degree Beaume adjustment to underflow
Next, utilizing the second potassium hydroxide solution to carry out degree Beaume adjustment to described underflow, is carry out stop growing the grain, to obtain the first solidliquid mixture after 50 to the degree Beaume of described underflow.Contriver is surprised to find, and when the degree Beaume of underflow is adjusted to 50, the amount of the potassium manganate crystal disproportionation reaction generation Manganse Dioxide of generation 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 second potassium hydroxide solution is not particularly limited.According to concrete examples more of the present invention, described second potassium hydroxide solution provides with the form of electrolysis mother liquor.Thereby, it is possible to recycle electrolysis mother liquor, improve the rate of recovery of potassium hydroxide, thus reach minimizing raw material consumption, reduce production cost, reduce discharging of waste liquid, the object of protection of the environment.
According to embodiments of the invention, the time stopping 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 stablized, and is convenient to subsequent operations.
S400: described first solidliquid mixture is carried out the first press filtration separation, to obtain solid mixture and press filtration waste liquid respectively
Next, the first solidliquid mixture obtained is carried out press filtration separation, to obtain solid mixture and press filtration waste liquid in step S300.Be separated the solid mixture obtained and be potassium manganate.Be separated containing a certain amount of potassium hydroxide in the press filtration waste liquid obtained, can recycle further.According to some embodiments of the present invention, mix with supernatant liquor after press filtration waste liquid evaporation can being concentrated, and add sheet alkali, prepare the first potassium hydroxide solution.According to other embodiments of the present invention, mix with supernatant liquor after press filtration waste liquid evaporation can being concentrated, preparation the 3rd potassium hydroxide solution.Thus, achieve the recycling of press filtration waste liquid, thus improve the rate of recovery of potassium hydroxide, decrease discharging of waste liquid, reach Jie Neng Jian Mao, the object of clean environment firendly.
The potassium manganate that above-mentioned steps prepares can through being further used for preparing potassium permanganate.Therefore, according to some embodiments of the present invention, the method preparing potassium manganate of the present invention is further comprising the steps:
The 3rd potassium hydroxide solution is utilized to carry out the process of tune liquid to potassium manganate, to obtain the second solidliquid mixture
Due in oxidation reaction process, side reaction SiO can be there is
2+ 2KOH=K
2siO
3+ H
2o, thus, also containing a small amount of K in the potassium manganate crystal prepared through abovementioned steps
2siO
3impurity, in order to obtain the higher potassium manganate of purity, can utilize the 3rd potassium hydroxide solution to carry out the process of tune liquid 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 then dissolve, and stays in solid phase, thus, further across solid-liquid separation, effectively can remove the potassium silicate impurity in potassium manganate.In addition, because potassium silicate has stronger absorption property, other impurity can be adsorbed further in the surface of solid silicic acid potassium, thus can purify potassium manganate further, and then obtains the higher potassium manganate solution of purity.
Second solidliquid mixture is carried out the second press filtration separation, to obtain potassium manganate solution and waste residue respectively
Then, the second solidliquid mixture is carried out press filtration separation, to obtain potassium manganate solution and waste residue.Thereby, it is possible to efficiently by the solid impurity removing in the second solidliquid mixture, obtain the potassium manganate solution that purity is higher, thus be conducive to the carrying out of subsequent step, raise the efficiency.
Potassium manganate solution is carried out 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 electrolysis, to make potassium manganate react 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 suction filtration, to obtain potassium permanganate coarse-grain and electrolysis mother liquor.As can be seen from above-mentioned reaction equation, containing a certain amount of potassium hydroxide in described electrolysis mother liquor, thus recycling can be carried out to it.According to some embodiments of the present invention, using electrolysis mother liquor directly as the second potassium hydroxide solution, degree Beaume adjustment can be carried out to described underflow.Thus, achieve the recycle of electrolysis mother liquor, thus reach raising raw material availability, reduce discharging of waste liquid, reduce costs, the object of protection of the environment.
Potassium permanganate coarse-grain is carried out complex crystallization and drying treatment successively, to obtain potassium permanganate crystals
Because in the potassium permanganate coarse-grain for preparing, the content of potassium permanganate is lower, thus need to carry out complex crystallization process 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, thus obtain the potassium permanganate crystals that crystal grain is larger, potassium permanganate content is higher.
Describe the method preparing potassium manganate of the present invention in detail with upper part, in order to the method can be understood better, below the equipment can implementing the method has been described in detail again.
According to a further aspect in the invention, present invention also offers 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 potassium manganate efficiently, and this structure of reactor is simple, easy to operate, and use clean energy, heat utilization efficiency is high, is easy to realize industrialization scale operation.
According to embodiments of the invention, reaction compartment is limited with in described body 100, described body 100 head clearance is provided with oxygen intake 101, useless oxygen outlet 102 and opening for feed 103, described body 100 middle and upper part is provided with discharge port 104, described oxygen intake 101 is for described reaction compartment delivering oxygen or oxygen-rich air, described useless oxygen outlet 102 is for discharging remaining oxygen in described reaction compartment and water vapour, described opening for feed 103 is for transfer ore pulp in described reaction compartment, the potassium manganate feed liquid that described discharge port 104 obtains after carrying out oxidizing reaction for the described ore pulp of discharging in described reaction compartment.
According to embodiments of the invention, described reactor 1000 has multiple oxygen intake 101.Thereby, it is possible to quick, a large amount of, oxygen or oxygen-rich air to be transported in reaction compartment and to make it be uniformly distributed in reaction compartment, ensureing well-oxygenated environment stronger in reaction compartment, thus improve the efficiency of oxidizing reaction.
According to embodiments of the invention, described ore pulp is that first potassium hydroxide solution of 45-70 % by weight and Manganse Dioxide are mixed by concentration.Thus, be conducive to Manganse Dioxide and fully react, improve the transformation efficiency of Manganse Dioxide, thus efficiently prepare potassium manganate.
According to embodiments of the invention, namely the source of described first potassium hydroxide solution and described Manganse Dioxide provides form to be not particularly limited.According to some embodiments of the present invention, described first potassium hydroxide solution utilizes sheet alkali to prepare and obtains, and described Manganse Dioxide provides with the form of pyrolusite.According to concrete examples more of the present invention, described first potassium hydroxide solution obtains by being concentrated by described press filtration waste liquid evaporation to mix with described supernatant liquor and add sheet alkali in mixed solution afterwards.Thereby, it is possible to by supernatant liquor recycle, improve the rate of recovery of potassium hydroxide, thus reach the object reducing reagent consumption, reduce costs.
According to embodiments of the invention, the ratio of described Manganse Dioxide and described 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 improve the transformation efficiency of Manganse Dioxide, and then improve the productive rate of 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 pressure is 0.2-1.2Mpa.Thus, can react under optimal pressure condition, be conducive to improving reaction efficiency.
According to embodiments of the invention, described ore pulp heating unit 200 is arranged in described body 100, for being carried out being heated to 250-260 degree Celsius by described ore pulp.According to embodiments of the invention, described ore pulp heating unit 200 is far infrared heater.Thereby, it is possible to effectively utilize clean energy to heat reaction raw materials, less to the pollution of environment, effects of energy conservation and environmental protection is more remarkable, and heat utilization efficiency is higher.
According to embodiments of the invention, it is inner that described whipping appts 300 is arranged at described body 100, for stirring described ore pulp.According to some embodiments of the present invention, described whipping appts 300 comprises stirring arm and is located at the multiple blades be spaced apart from each other on described stirring arm and along the axis of described stirring arm.Thus, be conducive to even for described flowsheet of slurry agitation.According to other embodiments 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 up of 718 alloys, and described blade is made up of Martensite Stainless Steel.Thus, stirring rake and paddle have good alkali corrosion resistance and oxygen corrosion performance, thus 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 embodiments 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 top, and with described oxygen intake 101, described useless oxygen export 102 and described opening for feed 103 interval arrange.
According to embodiments of the invention, with reference to Fig. 2 and Fig. 3, described reactor 1000 comprises further: oxygen heating arrangement 400, described oxygen heating arrangement 400 is communicated with described oxygen intake 101, for before the oxygen carried to described reaction compartment or oxygen-rich air, described oxygen or oxygen-rich air are carried out being preheated to 200 degrees Celsius.Thus, utilize oxygen heating arrangement 400, effectively oxygen or oxygen-rich air can be preheated to the temperature needed for oxidizing reaction, thus 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 comprises further: point device of air 500, described point of device of air 500 is connected with described multiple oxygen intake 101 with described oxygen heating arrangement 400 respectively, for being dispensed to each oxygen intake 101 by through the oxygen of described oxygen heating arrangement 400 preheating or oxygen-rich air.Thus, can efficiently oxygen or oxygen-rich air be transported in reaction compartment, maintain well-oxygenated environment stronger in reaction compartment, thus improve reaction efficiency.
According to embodiments of the invention, with reference to Fig. 2 and Fig. 3, described reactor 1000 comprises further: gas-liquid separator 600, described gas-liquid separator 600 has import, venting port and water port, described import exports 102 with described useless oxygen and is connected, described venting port is for discharging the oxygen after separation, described water port is connected with described reaction compartment, described gas-liquid separator is used for the described remaining oxygen of discharging from described useless oxygen outlet and water vapour to carry out gas-liquid separation, and by be separated after oxygen discharge described gas-liquid separator and by be separated after Liquid transfer give described reaction compartment.Thereby, it is possible to the water effectively carried by useless oxygen 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 comprises oxygen hose (not shown) further, described oxygen hose along described body 100 to be axially set in described body 100 inner, and be communicated with described oxygen intake 101, for the oxygen delivery that will enter from described oxygen intake 101 to described reaction compartment bottom.Thus, be conducive to ore pulp and fully contact with oxygen, thus 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 up of 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, present invention also offers 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 in oxygen enrichment atmosphere, in 250-260 degree Celsius, under 0.2-1.2Mpa, make concentration be that first potassium hydroxide solution of 60-75 % by weight and Manganse Dioxide carry 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 liquid from described reactor 1000, and described potassium manganate feed liquid is left standstill and carries out solid-liquid separation, to obtain supernatant liquor and underflow respectively; 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 adjustment to described underflow, be carry out stop growing the grain, to obtain the first solidliquid mixture after 50 to the degree Beaume of described underflow; Described first press filtration tripping device 4000 is connected with described stop rystallization device 3000, for receiving described first solidliquid mixture from described stop rystallization device 3000 and carrying out the first press filtration separation, to obtain solid mixture and press filtration waste liquid respectively, described solid mixture is described potassium manganate.Contriver is surprised to find, utilize the system preparing potassium manganate of the present invention, effectively can implement the method preparing potassium manganate of the present invention, and the technique that relates to of this system 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 carry out stopping time of growing the grain and 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 preparing potassium manganate comprises dosing unit (not shown) further, described dosing unit is connected with described reactor 1000, for preparing described first potassium hydroxide solution and add Manganse Dioxide to prepare ore pulp in described first potassium hydroxide solution, and by described pulp conveying to described reactor 1000.
According to embodiments of the invention, the described system preparing potassium manganate comprises supernatant liquor transfer lime (not shown) further, 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 first potassium hydroxide solution.
According to embodiments of the invention, the described system preparing potassium manganate comprises further: adjust liquid processing device (not shown), 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 first press filtration tripping device 4000, for receiving described potassium manganate from described first press filtration tripping device 4000, the 3rd potassium hydroxide solution is utilized to carry out the process of tune liquid to obtain the second solidliquid mixture to described potassium manganate, in described second solidliquid mixture, concentration of potassium hydroxide is 2-5 % by weight, and potassium manganate concentration is 120 ~ 150g/l; Described second press filtration tripping device is connected with described tune liquid processing device, for receiving described second solidliquid mixture from described tune liquid processing device and carrying out the second press filtration separation, to obtain potassium manganate solution and waste residue respectively; Described electrolyzer is connected with described second press filtration tripping device, for receiving described potassium manganate solution from described second press filtration tripping device, and described potassium manganate solution is carried out electrolysis, to obtain potassium permanganate feed liquid; Described Suction filtration device is connected with described electrolyzer, for receiving described potassium permanganate feed liquid from described electrolyzer, and described potassium permanganate feed liquid is carried out suction filtration process, 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 complex crystallization and drying treatment, successively to obtain potassium permanganate crystals.Thus, the impurity in potassium manganate coarse-grain can be removed, and the potassium manganate after can effectively utilizing removal of impurities prepares potassium permanganate.
According to embodiments of the invention, comprise electrolysis mother liquor transfer lime (not shown) further, 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, to carry out degree Beaume adjustment as described second potassium hydroxide solution to described underflow.Thereby, it is possible to by electrolysis disposing mother liquor recycle, thus reduce reagent consumption, reduce production cost, reduce discharging of waste liquid, protection of the environment.
According to embodiments of the invention, described 3rd potassium hydroxide solution obtains by being concentrated by described press filtration waste liquid evaporation to mix with described supernatant liquor afterwards.Thus, can 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 to discharge and contaminate environment, and then reach and reduce costs, Jie Neng Jian Mao, the object of clean environment firendly.
Referring to Fig. 2-4, further the reactor of the present invention under working order and system 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 to by opening for feed 103 in the reaction compartment of reactor 1000, oxygen is preheating to 200 degrees Celsius through oxygen heating arrangement 400(successively simultaneously), divide device of air 500, be passed in reaction compartment by oxygen intake 101, under whipping appts 300 carries out stirring and heating unit 200 carries out the condition heated, oxidizing reaction is there is in ore pulp and oxygen in reaction compartment, 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, following potassium manganate feed liquid is transported to equipment for separating liquid from solid 2000 through discharge port 104, solid-liquid separation is carried out in equipment for separating liquid from solid 2000, 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, after being regulated degree Beaume to 50 by the second potassium hydroxide solution, stop growing the grain is carried out in stop rystallization device 3000, obtain the first solidliquid mixture, first solidliquid mixture is transported to the first filter-pressing device 4000 and carries out press filtration separation subsequently, be separated the press filtration waste liquid obtained be transported to press filtration liquid waste tank (not shown) and be delivered to dosing unit for batching through press filtration waste liquid transfer lime, be separated the potassium manganate coarse-grain obtained and be transported to tune liquid processing device (not shown), adjust after liquid process through the 3rd potassium hydroxide solution, the second solidliquid mixture obtained is transported to the second press filtration tripping device (not shown) and carries out press filtration separation, be separated the filtrate obtained and be 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 through Cemented filling to adjusting liquid processing device, the potassium permanganate coarse-grain obtained is transported to complex crystallization device (not shown) and carries out complex crystallization and drying treatment, obtain potassium permanganate crystals thus.
Embodiment 1
Utilize the reactor shown in Fig. 2 or Fig. 3, and the system shown in Fig. 4, according to the foregoing method preparing potassium manganate, prepare potassium manganate in accordance with the following steps:
A. oxidizing reaction: concentration is that first potassium hydroxide solution of 45-70 % by weight is mixed to form ore pulp with pyrolusite according to the ratio that the potassium hydroxide mass ratio mixed in Manganse Dioxide and the first potassium hydroxide solution is 1:5-15, in oxygen enrichment atmosphere, 250-260 degree Celsius, under 0.2-1.2Mpa condition, carry out oxidizing reaction, to obtain potassium manganate feed liquid;
B. admittedly midnight from: after potassium manganate feed liquid leaves standstill appropriate time, carry out solid-liquid separation, to obtain supernatant liquor and underflow respectively;
C. stop growing the grain: utilize the second potassium hydroxide solution to carry out degree Beaume adjustment to underflow, be after 50 to the degree Beaume of underflow, carry out 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 obtained in step c is carried out press filtration separation, be separated the press filtration waste liquid obtained and be delivered to press filtration liquid waste tank, after evaporation concentration, for preparing the first potassium hydroxide solution and the 3rd potassium hydroxide solution, being separated the solid obtained is potassium manganate coarse-grain;
E. liquid process is adjusted: utilize the 3rd potassium hydroxide solution to carry out the process of tune liquid to the potassium manganate coarse-grain obtained in steps d, to obtain the second solidliquid mixture;
F. the second press filtration is separated: the second solidliquid mixture obtained in step e is carried out press filtration separation, to obtain potassium manganate solution and waste residue;
G. electrolysis: in electrolyzer, carry out electrolysis to the potassium manganate solution obtained in step f, potassium manganate is generated potassium permanganate by electrolysis, to obtain potassium permanganate feed liquid;
H. suction filtration: in Suction filtration device, suction filtration process is carried out to the potassium permanganate feed liquid obtained in step g, to obtain potassium permanganate coarse-grain and electrolysis mother liquor, be wherein used for preparing the second potassium hydroxide solution by electrolysis mother liquor conveying electrolysis mother liquor storage tank, the solid of acquisition is potassium permanganate coarse-grain;
I. complex crystallization and drying: in complex crystallization device, the potassium permanganate crystals obtained in step h, by water-soluble again, carries out complex crystallization, carries out drying treatment further, thus obtain industrial potassium permanganate to obtaining potassium permanganate crystals through complex crystallization.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although illustrate and describe embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple change, amendment, replacement and modification to these embodiments when not departing from principle of the present invention and aim, scope of the present invention is by claim and equivalents thereof.
Claims (5)
1. prepare a method for potassium manganate, it is characterized in that, comprise the following steps:
In oxygen enrichment atmosphere, 250-260 degree Celsius, under 0.2-1.2MPa, make concentration be that first potassium hydroxide solution of 45-70 % by weight and Manganse Dioxide carry out oxidizing reaction, to obtain potassium manganate feed liquid;
Described potassium manganate feed liquid is left standstill and carries out solid-liquid separation, to obtain supernatant liquor and underflow respectively;
Utilizing the second potassium hydroxide solution to carry out degree Beaume adjustment to described underflow, is carry out stop growing the grain, to obtain the first solidliquid mixture after 50 to the degree Beaume of described underflow; And
Described first solidliquid mixture is carried out the first press filtration separation, to obtain solid mixture and press filtration waste liquid respectively, described solid mixture is described potassium manganate,
Wherein, in described Manganse Dioxide and described first potassium hydroxide solution, the mass ratio of potassium hydroxide is 1:5-15.
2. method according to claim 1, is characterized in that, carries out described stop growing the grain at least 3 days.
3. method according to claim 1, is characterized in that, comprises further:
Utilize the 3rd potassium hydroxide solution to carry out the process of tune liquid to described potassium manganate, to obtain the second solidliquid mixture, in described second solidliquid mixture, concentration of potassium hydroxide is 2-5 % by weight, and potassium manganate concentration is 120 ~ 150g/L;
Described second solidliquid mixture is carried out the second press filtration separation, to obtain potassium manganate solution and waste residue respectively;
Described potassium manganate solution is carried out electrolysis and suction filtration successively, to obtain potassium permanganate coarse-grain and electrolysis mother liquor; And
Described potassium permanganate coarse-grain is carried out complex crystallization and drying treatment, successively to obtain potassium permanganate crystals.
4. method according to claim 3, is characterized in that, comprises further:
Described press filtration waste liquid evaporation is concentrated, and mixes with described supernatant liquor, to obtain described 3rd potassium hydroxide solution.
5. method according to claim 3, is characterized in that, described 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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| JPS6052095B2 (en) * | 1978-12-22 | 1985-11-18 | 日本曹達株式会社 | Production method of potassium manganate |
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