CN104357662B - A kind of harmless treatment process of electrolytic manganese residues - Google Patents
A kind of harmless treatment process of electrolytic manganese residues Download PDFInfo
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Abstract
The invention discloses the harmless treatment process of a kind of electrolytic manganese residues, wash away manganese slag including utilizationization pulp-water high pressure, make manganese slag substantially change slurry; The filter chamber inner filtration that manganese scorification serosity injects diaphragm filter press is obtained filter cake, under preloading condition, described filter cake is carried out two-stage acid leaching; Keep described preloading condition, multistage cleaning mixture is injected in described filter chamber and carries out multistage washing; The alkali liquor that pH is 9-10.5 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, in described filtrate channel, carries out interim inflation; After cured terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping. Adopt the technique that the application provides, the soluble manganese ions in electrolytic manganese residues can be extracted further, the manganese ion in filter cake is converted into insoluble manganese precipitation simultaneously, make the manganese ion of remaining in waste residue be unlikely in stacking process, penetrate in earth's surface and subsoil water, polluted underground water resource.
Description
Technical field
The present invention relates to the process technique of a kind of metal slag, be specifically related to the harmless treatment process of a kind of electrolytic manganese residues.
Background technology
Electrolytic manganese residues is the filtering residue adding sulfuric acid solution electrolysis production manganese in manganese carbonate breeze or manganese monoxide mineral powder, namely in reactor, add sulfuric acid solution react generation manganese sulfate with manganese carbonate breeze or manganese monoxide mineral powder, a small amount of reducing agent is added, by the Fe in solution when pH value is close to 42+Oxidation hydrolytic precipitation, again with acid excessive with reaction in liquefied ammonia, when pH value is close to 7, adding vulcanizing agent makes heavy metal ion in solution generate corresponding sulfide precipitation, then it is filtered with pressure filter, filtrate enters electrolyzer Inner electrolysis, the filter cake of discharge and electrolytic manganese residues, is a kind of waste residue containing manganese.
At present, China is several ten million tons of electrolytic manganese residues in tailings reservoir for piling, and this waste residue is faintly acid, complex chemical composition, wherein available Fe content is about 3%, and this shows that China there are about the promoter manganese of hundreds of thousands ton and is in waste state, additionally includes with ionic state NH4 +The ammonia nitrogen that form exists, the bulk deposition of manganese slag not only causes the serious waste of the raw material of industry, and deposit through long-term, some toxic heavy metal elements in waste residue are caused to be penetrated into by soil layer in earth's surface and subsoil water, affect groundwater resources, contaminated environment, human health is constituted a serious threat, therefore, the harmless treatment of electrolytic manganese residues has great importance.
Chinese patent literature CN103286116A discloses a kind of method of harmless treatment electrolytic manganese residues, it includes electrolytic manganese residues loads blender stirring, successively add sodium phosphate and calcium oxide, realize solidification and the removal of Soluble Manganese and ammonia nitrogen in manganese slag, thus realizing the innoxious of manganese slag, but owing to the stickiness of electrolytic manganese residues is bigger so that electrolytic manganese residues is difficult to crush, thus affect follow-up processing procedure. A kind of method that manganese slag harmlessness processes and comprehensively utilizes is disclosed for this Chinese patent literature CN101691633A, first manganese slag is washed by it, filter pressing, separate manganese sulfate and ammonium sulfate, then the slag washing water containing manganese sulfate and ammonium sulfate is reacted with precipitant, thus the manganese ion in slag washing water being converted into manganous hydroxide or manganese carbonate is precipitated out, reclaiming the solution after manganese to react with lime cream, making ammonium sulfate be converted into ammonia and calcium sulfate, thus realizing the innoxious of manganese slag.Also due to the high viscosity problem of electrolytic manganese residues, make manganese scorification slurry thoroughly cannot not realize innoxious, additionally, manganese slag is realized innoxious by diluting washing by above-mentioned technology, the required water yield consumed of its manganese scorification slurry is very big, and the cost manganese in washings and ammonia removed is sufficiently expensive.
Summary of the invention
For solving in prior art the very much not facilitated slurry of electrolytic manganese residues stickiness in electrolytic manganese residues harmless treatment process, and then affect the problem of follow-up post processing and change slurry and need to consume the problem of a large amount of water, and then the harmless treatment process of a kind of electrolytic manganese residues is provided.
For this, the technical scheme that the application takes is,
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizationization pulp-water high pressure washes away manganese slag, and after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag as changing pulp-water in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.3-0.5MPa;
(4) under preloading condition, two-stage nitration acid is injected in described filter chamber described filter cake is carried out two-stage acid leaching;
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage cleaning mixture is injected in described filter chamber and carries out multistage washing;
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.3-0.4MPa in described filtrate channel is blown;
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH is 9-10.5 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, in described filtrate channel, carry out interim inflation;
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in described step (2), when manganese concentration is not less than 30g/L in described filtrate, collects manganese concentration and be not less than the filtrate of 30g/L to reclaim manganese ion.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in described step (7), the solidification residual liquid flowed out in cured process adds alkali, and to adjust pH be 9-10.5, staticly settles, takes supernatant and be back to described step (7) as alkali liquor and carry out the cured of manganese ion.
In the harmless treatment process of above-mentioned electrolytic manganese residues, the 10-30wt% that injection rate is described filter cake quality of alkali liquor in described step (7), the injection pressure of described alkali liquor 0.05MPa higher than washing pressure, the time of described cured is 5-30min.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in the described cured process of described step (7), in described filtrate channel, carry out interim inflation, every minor tick 10min, inflation 1min, gas temperature 30-70 DEG C, gas pressure 0.3-0.4MPa.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in described step (4), the pressure that described two-stage nitration acid is injected is 0.3-0.5MPa, and the 20-150wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 10-30min.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in described step (5), the flow of described cleaning mixture is 5-20m3/ h, the pressure that cleaning mixture injects is 0.25-0.45MPa, and wash time is 5-30min.
In the harmless treatment process of above-mentioned electrolytic manganese residues, the gas flow of described air blowing is 5-20m3/ min, gas pressure is 0.3-0.4MPa, and gassing time is 1-5min.
Compared with prior art, the invention have the advantages that,
(1) harmless treatment process of the electrolytic manganese residues of the application offer is provided, the soluble manganese ions in electrolytic manganese residues can be extracted further, thus decreasing the waste of promoter manganese, manganese ion in electricity manganese manganese slag is extracted further, after manganese ion in filter cake being solidified simultaneously, in filter cake, the manganese ion of solubility is converted into insoluble manganese precipitation, so that the manganese ion of remaining is unlikely in stacking process in follow-up waste residue, penetrate in earth's surface and subsoil water, polluted underground water resource, threatens human health.
Owing to the viscosity of manganese slag is big, its innocent treatment procedure needs carry out break process, even if having crushed, traditional sizing process of changing still makes the change of manganese slag starch not thorough, thus affecting the treatment effect of manganese slag, and the manganese slag obtaining thoroughization slurry needs substantial amounts of water and certain broken fineness to realize, in the harmless treatment process of the electrolytic manganese residues that the application provides, utilizing washings high pressure to wash away manganese slag makes it substantially change slurry, without broken, even if there being bigger material to exist, after the later stage forms filter cake, by the process of two-stage acid leaching, the manganese slag that non-completion is starched is made to utilize the carbon dioxide produced as foaming agent in acidleach process, it is made to become loose, it is beneficial to cleaning mixture to penetrate, improve the strainability of filter cake, reach the effect uniformly penetrated, thus reducing slurry cost, manganese ion can also be extracted further simultaneously, reach the effect got twice the result with half the effort.
The harmless treatment process of the electrolytic manganese residues of the application offer is provided, through the technique such as acidleach and washing of early stage, the metal of solid-state in filter cake is converted into water miscible metal, and wash out together with ammonia nitrogen, change is significantly cut down in generation by filter cake quality, subsequent process injects the cured carrying out manganese ion in described filter chamber with the alkali liquor that pH value is 9-10.5, the soluble manganese ions remained in filter cake is converted into insoluble manganese precipitation, simultaneously, selecting pH value is the alkali liquor of 9-10.5 partly in order to guarantee finally to process the secondary manganese slag pH value obtained between 6-9, to meet the standard of country, coordinate simultaneously and adjust the parameter such as innoxious washing pressure and washing flow, prevent the solution between the diaphragm of pressure filter and filter cake and a large amount of molecule precipitation of the instantaneous generation of solution in filter cake pore, and coordinate the process of interim inflation, the molecule precipitation major part making generation carries out filter cake from solution, other be attached to filter cake, combine closely with filter cake, thus the problem solving the pore of blocking filter cloth and filter cake, technique is enable to be smoothed out, additionally, in the solidification process of manganese ion, the NH of remaining in filter cake4+Being converted into ammonia and be diffused in drainage system by the pore of filter cake, the discharge process of ammonia is conducive to dredging pore.
(2) harmless treatment process of the electrolytic manganese residues of the application offer is provided, the two-stage acid leaching process of electrolytic manganese residues can produce carbon dioxide, so that the physical arrangement of filter cake changes, make it loosely organized, and adopt the step of air blowing partly in order to take substantial amounts of residual liquid from filter cake out of, prior in order that make cured evenly.
Detailed description of the invention
The present invention the harmless treatment process of electrolytic manganese residues be applicable to all of electrolytic manganese residues, for purposes of illustration only, in following example and comparative example, the electrolytic manganese residues adopted is learnt from else's experience and measured wherein soluble manganese ions concentration is 36g/L (1.5wt%), NH4 +Content be 28g/L (1.2wt%).
Embodiment 1
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizing water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity, and in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.3MPa;
(4) under preloading condition, two-stage nitration acid being injected in described filter chamber and described filter cake carries out two-stage acid leaching, the pressure that described two-stage nitration acid is injected is 0.5MPa, and the 30wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 10min
(5) after described two-stage acid leaching terminates, keeping described preloading condition, injected in described filter chamber by multistage cleaning mixture and carry out multistage washing, the flow of described cleaning mixture is 20m3/ h, the pressure that cleaning mixture injects is 0.45MPa, and wash time is 25min.
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.3MPa in described filtrate channel is blown, and the gas flow of described air blowing is 8m3/ min, gas temperature is room temperature, and gassing time is 2min.
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH is 9 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, carrying out interim inflation in described filtrate channel, wherein, the injection rate of alkali liquor is the 25wt% of described filter cake quality, the injection pressure 0.5MPa of described alkali liquor, the time of described cured is 10min; In described filtrate channel, carry out interim inflation, every minor tick 10min, inflate 1min, gas temperature 40 DEG C, gas pressure 0.3MPa. The solidification residual liquid flowed out in cured process adds alkali, and to adjust pH be 9, staticly settles, takes supernatant and be back to this step as alkali liquor and carry out the cured of manganese ion.
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In this technical process, when described in described step (2), the manganese concentration of filtrate is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant, reclaims manganese ion, and the change pulp-water tap water lacked in step (1) supplements.
Embodiment 2
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizing water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity, and in mass, the consumption of described water is 4 times of described manganese slag amount;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.35MPa;
(4) under preloading condition, two-stage nitration acid being injected in described filter chamber and described filter cake carries out two-stage acid leaching, the pressure that described two-stage nitration acid is injected is 0.45MPa, and the 40wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 15min
(5) after described two-stage acid leaching terminates, keeping described preloading condition, injected in described filter chamber by multistage cleaning mixture and carry out multistage washing, the flow of described cleaning mixture is 15m3/ h, the pressure that cleaning mixture injects is 0.25MPa, and wash time is 30min.
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.4MPa in described filtrate channel is blown, and the gas flow of described air blowing is 10m3/ min, gas temperature is room temperature, and gassing time is 1min.
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH is 10 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, carrying out interim inflation in described filtrate channel, wherein, the injection rate of alkali liquor is the 20wt% of described filter cake quality, the injection pressure 0.3MPa of described alkali liquor, the time of described cured is 5min; In described filtrate channel, carry out interim inflation, every minor tick 10min, inflate 1min, gas temperature 30 DEG C, gas pressure 0.4MPa. The solidification residual liquid flowed out in cured process adds alkali, and to adjust pH be 10, staticly settles, takes supernatant and be back to this step as alkali liquor and carry out the cured of manganese ion.
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In this technical process, when described in described step (2), the manganese concentration of filtrate is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Embodiment 3
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizing water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity, and in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.4MPa;
(4) under preloading condition, two-stage nitration acid being injected in described filter chamber and described filter cake carries out two-stage acid leaching, the pressure that described two-stage nitration acid is injected is 0.35MPa, and the 60wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 20min
(5) after described two-stage acid leaching terminates, keeping described preloading condition, injected in described filter chamber by multistage cleaning mixture and carry out multistage washing, the flow of described cleaning mixture is 10m3/ h, the pressure that cleaning mixture injects is 0.35MPa, and wash time is 20min.
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.35MPa in described filtrate channel is blown, and the gas flow of described air blowing is 10m3/ min, gas temperature is room temperature, and gassing time is 5min.
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH is 9.5 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, carrying out interim inflation in described filtrate channel, wherein, the injection rate of alkali liquor is the 15wt% of described filter cake quality, the injection pressure 0.4MPa of described alkali liquor, the time of described cured is 20min; In described filtrate channel, carry out interim inflation, every minor tick 10min, inflate 1min, gas temperature 60 DEG C, gas pressure 0.35MPa. The solidification residual liquid flowed out in cured process adds alkali, and to adjust pH be 9.5, staticly settles, takes supernatant and be back to this step as alkali liquor and carry out the cured of manganese ion.
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In this technical process, when described in described step (2), the manganese concentration of filtrate is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Embodiment 4
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizing water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity, and in mass, the consumption of described water is 4 times of described manganese slag amount;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.45MPa;
(4) under preloading condition, two-stage nitration acid being injected in described filter chamber and described filter cake carries out two-stage acid leaching, the pressure that described two-stage nitration acid is injected is 0.3MPa, and the 80wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 30min
(5) after described two-stage acid leaching terminates, keeping described preloading condition, injected in described filter chamber by multistage cleaning mixture and carry out multistage washing, the flow of described cleaning mixture is 5m3/ h, the pressure that cleaning mixture injects is 0.3MPa, and wash time is 15min.
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.4MPa in described filtrate channel is blown, and the gas flow of described air blowing is 8m3/ min, gas temperature is room temperature, and gassing time is 3min.
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH is 10.5 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, carrying out interim inflation in described filtrate channel, wherein, the injection rate of alkali liquor is the 10wt% of described filter cake quality, the injection pressure 0.35MPa of described alkali liquor, the time of described cured is 30min; In described filtrate channel, carry out interim inflation, every minor tick 10min, inflate 1min, gas temperature 50 DEG C, gas pressure 0.4MPa. The solidification residual liquid flowed out in cured process adds alkali, and to adjust pH be 10.5, staticly settles, takes supernatant and be back to this step as alkali liquor and carry out the cured of manganese ion.
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In this technical process, when described in described step (2), the manganese concentration of filtrate is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Embodiment 5
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizing water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity, and in mass, the consumption of described water is 3.5 times of described manganese slag amount;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.5MPa;
(4) under preloading condition, two-stage nitration acid being injected in described filter chamber and described filter cake carries out two-stage acid leaching, the pressure that described two-stage nitration acid is injected is 0.4MPa, and the 75wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 25min
(5) after described two-stage acid leaching terminates, keeping described preloading condition, injected in described filter chamber by multistage cleaning mixture and carry out multistage washing, the flow of described cleaning mixture is 15m3/ h, the pressure that cleaning mixture injects is 0.4MPa, and wash time is 5min.
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.3MPa in described filtrate channel is blown, and the gas flow of described air blowing is 7m3/ min, gas temperature is room temperature, and gassing time is 5min.
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH is 10.5 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, carrying out interim inflation in described filtrate channel, wherein, the injection rate of alkali liquor is the 30wt% of described filter cake quality, the injection pressure 0.45MPa of described alkali liquor, the time of described cured is 25min; In described filtrate channel, carry out interim inflation, every minor tick 10min, inflate 1min, gas temperature 70 DEG C, gas pressure 0.3MPa. The solidification residual liquid flowed out in cured process adds alkali, and to adjust pH be 10.5, staticly settles, takes supernatant and be back to this step as alkali liquor and carry out the cured of manganese ion.
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In this technical process, when described in described step (2), the manganese concentration of filtrate is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Embodiment 6
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizing water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity, and in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.5MPa;
(4) under preloading condition, two-stage nitration acid being injected in described filter chamber and described filter cake carries out two-stage acid leaching, the pressure that described two-stage nitration acid is injected is 0.4MPa, and the 150wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 10min
(5) after described two-stage acid leaching terminates, keeping described preloading condition, injected in described filter chamber by multistage cleaning mixture and carry out multistage washing, the flow of described cleaning mixture is 15m3/ h, the pressure that cleaning mixture injects is 0.4MPa, and wash time is 25min.
(6) after described washing terminates, keeping described preloading condition, the gas at normal temperature passing into 0.4MPa in described filtrate channel is blown, and the gas flow of described air blowing is 15m3/ min, gassing time is 4min.
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH is 9 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, carrying out interim inflation in described filtrate channel, wherein, the injection rate of alkali liquor is the 25wt% of described filter cake quality, the injection pressure 0.45MPa of described alkali liquor, the time of described cured is 30min;In described filtrate channel, carry out interim inflation, every minor tick 10min, inflate 1min, gas temperature 60 DEG C, gas pressure 0.35MPa. The solidification residual liquid flowed out in cured process adds alkali, and to adjust pH be 9, staticly settles, takes supernatant and be back to this step as alkali liquor and carry out the cured of manganese ion.
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In this technical process, when described in described step (2), the manganese concentration of filtrate is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Comparative example 1
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizing water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity, and in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.4MPa;
(4) under preloading condition, two-stage nitration acid being injected in described filter chamber and described filter cake carries out two-stage acid leaching, the pressure that described two-stage nitration acid is injected is 0.35MPa, and the 60wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 20min
(5) after described two-stage acid leaching terminates, keeping described preloading condition, injected in described filter chamber by multistage cleaning mixture and carry out multistage washing, the flow of described cleaning mixture is 10m3/ h, the pressure that cleaning mixture injects is 0.35MPa, and wash time is 20min.
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.35MPa in described filtrate channel is blown, and the gas flow of described air blowing is 6m3/ min, gas temperature is room temperature, and gassing time is 3min.
(7) after air blowing treatment terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(8) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In this technical process, when described in described step (2), the manganese concentration of filtrate is not less than 30g/L, described filtrate enters electrolytic manganese car liquid.
Comparative example 2
The harmless treatment process of a kind of electrolytic manganese residues, comprises the steps,
(1) utilizing water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity, and in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.6MPa;
(4) under preloading condition, two-stage nitration acid being injected in described filter chamber and described filter cake carries out two-stage acid leaching, the pressure that described two-stage nitration acid is injected is 0.2MPa, and the 200wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 60min
(5) after described two-stage acid leaching terminates, keeping described preloading condition, injected in described filter chamber by multistage cleaning mixture and carry out multistage washing, the flow of described cleaning mixture is 2m3/ h, the pressure that cleaning mixture injects is 0.5MPa, and wash time is 60min.
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.5MPa in described filtrate channel is blown, and the gas flow of described air blowing is 20m3/ min, gas temperature is room temperature, and gassing time is 30min.
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH is 9.5 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, carrying out interim inflation in described filtrate channel, wherein, the injection rate of alkali liquor is the 15wt% of described filter cake quality, the injection pressure 0.4MPa of described alkali liquor, the time of described cured is 20min; The solidification residual liquid flowed out in cured process adds alkali, and to adjust pH be 9.5, staticly settles, takes supernatant and be back to this step as alkali liquor and carry out the cured of manganese ion.
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
In this technical process, when described in described step (2), the manganese concentration of filtrate is not less than 30g/L, described filtrate enters electrolytic manganese car liquid.
Observe and above-described embodiment and comparative example process the pattern of the manganese slag obtained and it is detected, measure wherein soluble manganese ions and NH4 +Content, result is as shown in the table,
Obviously, above-described embodiment is only for clearly demonstrating example, and is not the restriction to embodiment. For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description. Here without also cannot all of embodiment be given exhaustive. And the apparent change thus extended out or variation are still among the protection domain of the invention.
Claims (7)
1. a harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilizationization pulp-water high pressure washes away manganese slag, and after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtains manganese scorification serosity;
(2) the filter chamber inner filtration that the pressurization of described manganese scorification serosity is injected diaphragm filter press obtains filter cake, and filtrate returns described step (1) and washes away manganese slag as changing pulp-water in order to high pressure;
(3) described filter cake being carried out precompressed, preload pressure is 0.3-0.5MPa;
(4) under preloading condition, two-stage nitration acid is injected in described filter chamber described filter cake is carried out two-stage acid leaching;
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage cleaning mixture is injected in described filter chamber and carries out multistage washing;
(6) after described washing terminates, keeping described preloading condition, the gas passing into 0.3-0.4MPa in described filtrate channel is blown;
(7) after described air blowing terminates, keep described preloading condition, the alkali liquor that pH value is 9-10.5 is injected the cured carrying out manganese ion in described filter chamber, in described cured process, in described filtrate channel, carry out interim inflation, every minor tick 10min, inflate 1min, gas temperature 30-70 DEG C, gas pressure 0.3-0.4MPa;
(8) after cured terminates, keep described preloading condition, pass into gas to the pan feeding passage of described diaphragm filter press along the end of feedstock direction and carry out blowback;
(9) after blowback terminates, the material in described filter chamber being carried out high pressure filter pressing, filter pressing terminates rear slag dumping.
2. the harmless treatment process of electrolytic manganese residues according to claim 1, it is characterised in that in described step (2), when manganese concentration is not less than 30g/L in described filtrate, collects manganese concentration and is not less than the filtrate of 30g/L to reclaim manganese ion.
3. the harmless treatment process of electrolytic manganese residues according to claim 1 and 2, it is characterized in that, in described step (7), it is 9-10.5 that the solidification residual liquid flowed out in cured process adds alkali adjustment pH value, staticly settle, take supernatant and be back to described step (7) as alkali liquor and carry out the cured of manganese ion.
4. the harmless treatment process of electrolytic manganese residues according to claim 3, it is characterized in that, the 10-30wt% that injection rate is described filter cake quality of alkali liquor in described step (7), the injection pressure of described alkali liquor 0.05MPa higher than washing pressure, the time of described cured is 5-30min.
5. the harmless treatment process of electrolytic manganese residues according to claim 4, it is characterized in that, in described step (4), the pressure that described two-stage nitration acid is injected is 0.3-0.5MPa, the 20-150wt% that injection rate is described filter cake weight of described two-stage nitration acid, the two-stage acid leaching time is 10-30min.
6. the harmless treatment process of electrolytic manganese residues according to claim 5, it is characterised in that in described step (5), the flow of described cleaning mixture is 5-20m3/ h, the pressure that cleaning mixture injects is 0.25-0.45MPa, and wash time is 5-30min.
7. the harmless treatment process of the electrolytic manganese residues according to claim 1,2,4,5 or 6, it is characterised in that the gas flow of described air blowing is 5-20m3/ min, gas pressure is 0.3-0.4MPa, and gassing time is 1-5min.
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| CN105274580B (en) * | 2015-11-15 | 2018-01-12 | 王兆兵 | The method that electrolytic manganese produces reclaimed water and manganese slag for comprehensive utilizes |
| CN106244802A (en) * | 2016-08-31 | 2016-12-21 | 中信大锰矿业有限责任公司 | A kind of method that manganese in electrolytic manganese residues reclaims |
| CN106927507B (en) * | 2017-03-29 | 2018-05-22 | 湘潭市环境保护科学研究院 | A kind of electrolysis MnO2With the method that waste residue containing Mn prepares manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer in electrolysis Mn productions |
| CN108689671B (en) * | 2018-06-07 | 2020-12-04 | 广西壮族自治区环境保护科学研究院 | Method for treating and recovering manganese and ammonium sulfate in electrolytic manganese slag |
| CN109811148B (en) * | 2019-01-31 | 2021-05-14 | 贵州大学 | Method for recovering soluble sulfate by piling and washing manganic acid leaching residues |
| CN110551898B (en) * | 2019-09-16 | 2021-07-06 | 中信大锰矿业有限责任公司 | Treatment method of electrolytic manganese slag |
| CN110642560A (en) * | 2019-11-21 | 2020-01-03 | 石晶 | Electrolytic manganese slag non-sintered brick and preparation method thereof |
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| JP5229416B1 (en) * | 2011-06-29 | 2013-07-03 | Ｊｆｅスチール株式会社 | Manganese recovery method |
| CN102503205A (en) * | 2011-11-04 | 2012-06-20 | 卿富安 | New formula and process method for preparing electrolytic manganese slag brick |
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