CN104357662A - Hazard-free treatment technology for electrolytic manganese residues - Google Patents
Hazard-free treatment technology for electrolytic manganese residues Download PDFInfo
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Abstract
The invention discloses a hazard-free treatment technology for electrolytic manganese residues. The technology comprises the following steps: washing the manganese residues in a high-pressure manner by using slurry water, and basically enabling the manganese residues to form slurry liquid; injecting the manganese residue slurry liquid into a filter chamber of a membrane press filter to be filtered to obtain a filter cake, and performing two-section acid leaching on the filter cake under a prepressing state; keeping the prepressing state, and injecting multi-stage washing liquid into the filter chamber to be washed in a multi-section manner; injecting alkali liquid of which the pH is 9 to 10.5 into the filter chamber to solidify manganese ions, and inflating the air into a filter liquid passage in a stage manner during the solidifying treatment; performing the high-pressure press filtering on substances in the filter chamber, and after the solidifying treatment is finished, discharging the residues. Through the adoption of the technology provided by the invention, the soluble manganese ions in the electrolytic manganese residues can be further extracted, and at the same time, the manganese ions in the filter cake are converted into the insoluble manganese to be deposited, so that the remained manganese ions in the waste residues cannot be permeated into the ground surface or the underground water to pollute the underground water resources in the stacking process.
Description
Technical field
The present invention relates to a kind for the treatment of process of metal slag, be specifically related to a kind of harmless treatment process of electrolytic manganese residues.
Background technology
Electrolytic manganese residues is the filter residue adding sulphuric acid soln electrolysis production manganese in manganous carbonate breeze or manganese monoxide mineral powder, namely in reactor, add sulphuric acid soln and manganous carbonate breeze or manganese monoxide mineral powder react and generate manganous sulfate, until pH value close to 4 time add a small amount of reductive agent, by the Fe in solution
2+oxidation is hydrolytic precipitation also, use the acid that liquefied ammonia neutralization reaction is excessive again, when pH value close to 7 time, adding vulcanizing agent makes heavy metal ion in solution generate corresponding sulfide precipitation, then filter 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 slightly acidic, complex chemical composition, Fe content wherein can be utilized about 3%, and this shows that China about has the promoter manganese of hundreds of thousands of ton to be in waste state, comprises with ionic state NH in addition
4 +the ammonia nitrogen that form exists, the bulk deposition of manganese slag not only causes the serious waste of industrial raw material, and deposit through long-term, some toxic heavy metal elements in waste residue are caused to penetrate in earth's surface and underground water by soil layer, affect groundwater resource, contaminate 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 comprises and electrolytic manganese residues is loaded stirrer stirring, successively add sodium phosphate and calcium oxide, realize solidification and the removal of Soluble Manganese and ammonia nitrogen in manganese slag, thus realize the innoxious of manganese slag, but because the stickiness of electrolytic manganese residues is comparatively large, makes electrolytic manganese residues be difficult to fragmentation, thus affect follow-up treating processes.Chinese patent literature CN101691633A discloses the method for the process of a kind of manganese slag harmlessness and comprehensive utilization for this reason, first it wash manganese slag, press filtration, be separated manganous sulfate and ammonium sulfate, then the slag washing water containing manganous sulfate and ammonium sulfate and precipitation agent are reacted, thus the mn ion in slag washing water is converted into manganous hydroxide or manganous carbonate is precipitated out, solution after recovery manganese and milk of lime react, and make ammonium sulfate be converted into ammonia and calcium sulfate, thus realize the innoxious of manganese slag.Equally due to the high viscosity problem of electrolytic manganese residues, make manganese scorification slurry thoroughly cannot not realize innoxious, in addition, manganese slag realizes innoxious by dilution washing by above-mentioned technology, the required water yield consumed of its manganese scorification slurry is very big, and the cost manganese in washing water and ammonia removed is very expensive.
Summary of the invention
Greatly not easily change slurry for solving in prior art electrolytic manganese residues stickiness in electrolytic manganese residues harmless treatment process, and then affect the problem of follow-up aftertreatment and change slurry and need to consume a large amount of water problem, and then a kind of harmless treatment process of electrolytic manganese residues is provided.
For this reason, the technical scheme that the application takes is,
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 slurries;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag as change pulp-water in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.3-0.5MPa;
(4) under preloading condition, two sections of acid are injected in described filter chamber two-stage acid leaching is carried out to described filter cake;
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing;
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.3-0.4MPa in described filtrate channel is blown;
(7) after described air blowing terminates, keeping described preloading condition, is that the alkali lye of 9-10.5 injects the solidification treatment that described filter chamber carries out mn ion by pH, in described solidification treatment process, carries out stage inflation in described filtrate channel;
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration 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 mn ion.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in described step (7), it is 9-10.5 that the solidification raffinate flowed out in solidification treatment process adds alkali adjustment pH, staticly settles, gets supernatant liquor and be back to as alkali lye the solidification treatment that described step (7) carries out mn ion.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in described step (7), the injection rate of alkali lye is the 10-30wt% of described filter cake quality, the injection pressure of described alkali lye is than washing pressure height 0.05MPa, and the time of described solidification treatment is 5-30min.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in the described solidification treatment process of described step (7), in described filtrate channel, carry out stage inflation, every minor tick 10min, inflation 1min, gas temperature 30-70 DEG C, gaseous tension 0.3-0.4MPa.
In the harmless treatment process of above-mentioned electrolytic manganese residues, in described step (4), the pressure that described two sections of acid are injected are 0.3-0.5MPa, and described two sections of sour injection rates are the 20-150wt% of described filter cake weight, and 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 washings is 5-20m
3/ h, the pressure that washings injects is 0.25-0.45MPa, and washing time is 5-30min.
In the harmless treatment process of above-mentioned electrolytic manganese residues, the gas flow of described air blowing is 5-20m
3/ min, gaseous tension is 0.3-0.4MPa, and gassing time is 1-5min.
Compared with prior art, tool of the present invention has the following advantages,
(1) harmless treatment process of the electrolytic manganese residues adopting the application to provide, the soluble manganese ions in electrolytic manganese residues can be extracted further, thus decrease the waste of promoter manganese, mn ion in electricity manganese manganese slag is extracted further, after mn ion in filter cake being cured simultaneously, in filter cake, the mn ion of solubility is converted into insoluble manganese precipitation, thus make mn ion remaining in follow-up waste residue be unlikely in stacking process, penetrate in earth's surface and underground water, polluted underground water resource, threatens human health.
Because the viscosity of manganese slag is large, need in its innocent treatment procedure to carry out break process, even if carried out fragmentation, it is not thorough that traditional change sizing process still makes the change of manganese slag starch, thus affect the treatment effect of manganese slag, and the manganese slag that will obtain thoroughization slurry needs a large amount of water and certain broken fineness to realize, in the harmless treatment process of the electrolytic manganese residues that the application provides, utilizing washing water high pressure to wash away manganese slag makes it substantially change slurry, without the need to fragmentation, even if there be larger to expect 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 utilizes the carbonic acid gas produced as whipping agent in acidleach process, it is made to become loose, be beneficial to washings to penetrate, improve the strainability of filter cake, reach the effect evenly penetrated, thus reducing slurry cost, mn ion can also be extracted further simultaneously, reach the effect of getting twice the result with half the effort.
The harmless treatment process of the electrolytic manganese residues adopting the application to provide, passing through the techniques such as acidleach in earlier stage and washing is water miscible metal by convert metals solid-state in filter cake, and wash out together with ammonia nitrogen, generation is significantly cut down change by filter cake quality, inject with the alkali lye that pH value is 9-10.5 the solidification treatment that described filter chamber carries out mn ion in subsequent process, the soluble manganese ions remained in filter cake is converted into insoluble manganese precipitation, simultaneously, select pH value to be the alkali lye of 9-10.5 to be on the one hand in order to ensure finally processing the secondary manganese slag pH value that obtains between 6-9, to meet the standard of country, coordinate the parameter such as the innoxious washing pressure of adjustment and washing flow simultaneously, prevent a large amount of molecule precipitation of the instantaneous generation of solution in the solution between the diaphragm of pressure filter and filter cake and filter cake pore, and coordinate the process of interim inflation, make the molecule of generation precipitate major part and carry out filter cake from solution, other be attached to filter cake, combine closely with filter cake, thus solve the problem of the pore of blocking filter cloth and filter cake, technique is carried out smoothly, in addition, in the solidification process of mn ion, NH remaining in filter cake
4+can be converted into ammonia is diffused in drainage system by the pore of filter cake, and the discharge process of ammonia is conducive to dredging pore.
(2) harmless treatment process of the electrolytic manganese residues adopting the application to provide, carbon dioxide can be produced in the two-stage acid leaching process of electrolytic manganese residues, thus the physical structure of filter cake is changed, make it loosely organized, and adopt the step of blowing to be on the one hand to take a large amount of residual liquids from filter cake out of, prior object be in order to make solidification treatment evenly.
Embodiment
The present invention the harmless treatment process of electrolytic manganese residues be applicable to all electrolytic manganese residues, for ease of illustrating, in following examples 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%), NH
4 +content be 28g/L (1.2wt%).
Embodiment 1
A harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilize water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtain manganese scorification slurries, in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.3MPa;
(4) under preloading condition, two sections of acid injected in described filter chambers and carry out two-stage acid leaching to described filter cake, the pressure that described two sections of acid are injected are 0.5MPa, and described two sections of sour injection rates are the 30wt% of described filter cake weight, and the two-stage acid leaching time is 10min
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing, the flow of described washings is 20m
3/ h, the pressure that washings injects is 0.45MPa, and washing time is 25min.
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.3MPa in described filtrate channel is blown, and the gas flow of described air blowing is 8m
3/ min, gas temperature is normal temperature, and gassing time is 2min.
(7) after described air blowing terminates, keep described preloading condition, by pH be 9 alkali lye inject the solidification treatment that described filter chamber carries out mn ion, in described solidification treatment process, in described filtrate channel, carry out stage inflation, wherein, the injection rate of alkali lye is the 25wt% of described filter cake quality, the injection pressure 0.5MPa of described alkali lye, the time of described solidification treatment is 10min; Stage inflation is carried out, every minor tick 10min, inflation 1min, gas temperature 40 DEG C, gaseous tension 0.3MPa in described filtrate channel.It is 9 that the solidification raffinate flowed out in solidification treatment process adds alkali adjustment pH, staticly settles, gets supernatant liquor and be back to as alkali lye the solidification treatment that this step carries out mn ion.
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
In this technological process, when the manganese concentration of filtrate described in described step (2) is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant, reclaims mn ion, and the change pulp-water tap water lacked in step (1) supplements.
Embodiment 2
A harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilize water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtain manganese scorification slurries, in mass, the consumption of described water is 4 times of described manganese slag amount;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.35MPa;
(4) under preloading condition, two sections of acid injected in described filter chambers and carry out two-stage acid leaching to described filter cake, the pressure that described two sections of acid are injected are 0.45MPa, and described two sections of sour injection rates are the 40wt% of described filter cake weight, and the two-stage acid leaching time is 15min
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing, the flow of described washings is 15m
3/ h, the pressure that washings injects is 0.25MPa, and washing time is 30min.
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.4MPa in described filtrate channel is blown, and the gas flow of described air blowing is 10m
3/ min, gas temperature is normal temperature, and gassing time is 1min.
(7) after described air blowing terminates, keep described preloading condition, by pH be 10 alkali lye inject the solidification treatment that described filter chamber carries out mn ion, in described solidification treatment process, in described filtrate channel, carry out stage inflation, wherein, the injection rate of alkali lye is the 20wt% of described filter cake quality, the injection pressure 0.3MPa of described alkali lye, the time of described solidification treatment is 5min; Stage inflation is carried out, every minor tick 10min, inflation 1min, gas temperature 30 DEG C, gaseous tension 0.4MPa in described filtrate channel.It is 10 that the solidification raffinate flowed out in solidification treatment process adds alkali adjustment pH, staticly settles, gets supernatant liquor and be back to as alkali lye the solidification treatment that this step carries out mn ion.
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
In this technological process, when the manganese concentration of filtrate described in described step (2) is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Embodiment 3
A harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilize water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtain manganese scorification slurries, in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.4MPa;
(4) under preloading condition, two sections of acid injected in described filter chambers and carry out two-stage acid leaching to described filter cake, the pressure that described two sections of acid are injected are 0.35MPa, and described two sections of sour injection rates are the 60wt% of described filter cake weight, and the two-stage acid leaching time is 20min
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing, the flow of described washings is 10m
3/ h, the pressure that washings injects is 0.35MPa, and washing time is 20min.
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.35MPa in described filtrate channel is blown, and the gas flow of described air blowing is 10m
3/ min, gas temperature is normal temperature, and gassing time is 5min.
(7) after described air blowing terminates, keep described preloading condition, by pH be 9.5 alkali lye inject the solidification treatment that described filter chamber carries out mn ion, in described solidification treatment process, in described filtrate channel, carry out stage inflation, wherein, the injection rate of alkali lye is the 15wt% of described filter cake quality, the injection pressure 0.4MPa of described alkali lye, the time of described solidification treatment is 20min; Stage inflation is carried out, every minor tick 10min, inflation 1min, gas temperature 60 DEG C, gaseous tension 0.35MPa in described filtrate channel.It is 9.5 that the solidification raffinate flowed out in solidification treatment process adds alkali adjustment pH, staticly settles, gets supernatant liquor and be back to as alkali lye the solidification treatment that this step carries out mn ion.
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
In this technological process, when the manganese concentration of filtrate described in described step (2) is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Embodiment 4
A harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilize water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtain manganese scorification slurries, in mass, the consumption of described water is 4 times of described manganese slag amount;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.45MPa;
(4) under preloading condition, two sections of acid injected in described filter chambers and carry out two-stage acid leaching to described filter cake, the pressure that described two sections of acid are injected are 0.3MPa, and described two sections of sour injection rates are the 80wt% of described filter cake weight, and the two-stage acid leaching time is 30min
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing, the flow of described washings is 5m
3/ h, the pressure that washings injects is 0.3MPa, and washing time is 15min.
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.4MPa in described filtrate channel is blown, and the gas flow of described air blowing is 8m
3/ min, gas temperature is normal temperature, and gassing time is 3min.
(7) after described air blowing terminates, keep described preloading condition, by pH be 10.5 alkali lye inject the solidification treatment that described filter chamber carries out mn ion, in described solidification treatment process, in described filtrate channel, carry out stage inflation, wherein, the injection rate of alkali lye is the 10wt% of described filter cake quality, the injection pressure 0.35MPa of described alkali lye, the time of described solidification treatment is 30min; Stage inflation is carried out, every minor tick 10min, inflation 1min, gas temperature 50 DEG C, gaseous tension 0.4MPa in described filtrate channel.It is 10.5 that the solidification raffinate flowed out in solidification treatment process adds alkali adjustment pH, staticly settles, gets supernatant liquor and be back to as alkali lye the solidification treatment that this step carries out mn ion.
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
In this technological process, when the manganese concentration of filtrate described in described step (2) is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Embodiment 5
A harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilize water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtain manganese scorification slurries, in mass, the consumption of described water is 3.5 times of described manganese slag amount;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.5MPa;
(4) under preloading condition, two sections of acid injected in described filter chambers and carry out two-stage acid leaching to described filter cake, the pressure that described two sections of acid are injected are 0.4MPa, and described two sections of sour injection rates are the 75wt% of described filter cake weight, and the two-stage acid leaching time is 25min
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing, the flow of described washings is 15m
3/ h, the pressure that washings injects is 0.4MPa, and washing time is 5min.
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.3MPa in described filtrate channel is blown, and the gas flow of described air blowing is 7m
3/ min, gas temperature is normal temperature, and gassing time is 5min.
(7) after described air blowing terminates, keep described preloading condition, by pH be 10.5 alkali lye inject the solidification treatment that described filter chamber carries out mn ion, in described solidification treatment process, in described filtrate channel, carry out stage inflation, wherein, the injection rate of alkali lye is the 30wt% of described filter cake quality, the injection pressure 0.45MPa of described alkali lye, the time of described solidification treatment is 25min; Stage inflation is carried out, every minor tick 10min, inflation 1min, gas temperature 70 DEG C, gaseous tension 0.3MPa in described filtrate channel.It is 10.5 that the solidification raffinate flowed out in solidification treatment process adds alkali adjustment pH, staticly settles, gets supernatant liquor and be back to as alkali lye the solidification treatment that this step carries out mn ion.
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
In this technological process, when the manganese concentration of filtrate described in described step (2) is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Embodiment 6
A harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilize water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtain manganese scorification slurries, in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.5MPa;
(4) under preloading condition, two sections of acid injected in described filter chambers and carry out two-stage acid leaching to described filter cake, the pressure that described two sections of acid are injected are 0.4MPa, and described two sections of sour injection rates are the 150wt% of described filter cake weight, and the two-stage acid leaching time is 10min
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing, the flow of described washings is 15m
3/ h, the pressure that washings injects is 0.4MPa, and washing time is 25min.
(6) after described washing terminates, keep 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 15m
3/ min, gassing time is 4min.
(7) after described air blowing terminates, keep described preloading condition, by pH be 9 alkali lye inject the solidification treatment that described filter chamber carries out mn ion, in described solidification treatment process, in described filtrate channel, carry out stage inflation, wherein, the injection rate of alkali lye is the 25wt% of described filter cake quality, the injection pressure 0.45MPa of described alkali lye, the time of described solidification treatment is 30min; Stage inflation is carried out, every minor tick 10min, inflation 1min, gas temperature 60 DEG C, gaseous tension 0.35MPa in described filtrate channel.It is 9 that the solidification raffinate flowed out in solidification treatment process adds alkali adjustment pH, staticly settles, gets supernatant liquor and be back to as alkali lye the solidification treatment that this step carries out mn ion.
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
In this technological process, when the manganese concentration of filtrate described in described step (2) is not less than 30g/L, described filtrate enters electrolytic manganese liquid plant.
Comparative example 1
A harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilize water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtain manganese scorification slurries, in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.4MPa;
(4) under preloading condition, two sections of acid injected in described filter chambers and carry out two-stage acid leaching to described filter cake, the pressure that described two sections of acid are injected are 0.35MPa, and described two sections of sour injection rates are the 60wt% of described filter cake weight, and the two-stage acid leaching time is 20min
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing, the flow of described washings is 10m
3/ h, the pressure that washings injects is 0.35MPa, and washing time is 20min.
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.35MPa in described filtrate channel is blown, and the gas flow of described air blowing is 6m
3/ min, gas temperature is normal 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, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
In this technological process, when the manganese concentration of filtrate described in described step (2) is not less than 30g/L, described filtrate enters electrolytic manganese car liquid.
Comparative example 2
A harmless treatment process for electrolytic manganese residues, comprises the steps,
(1) utilize water high pressure to wash away manganese slag, after making manganese slag substantially change slurry, injectionization stock tank stirs, and obtain manganese scorification slurries, in mass, the consumption of described water is 3 times of described manganese slag amount;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.6MPa;
(4) under preloading condition, two sections of acid injected in described filter chambers and carry out two-stage acid leaching to described filter cake, the pressure that described two sections of acid are injected are 0.2MPa, and described two sections of sour injection rates are the 200wt% of described filter cake weight, and the two-stage acid leaching time is 60min
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing, the flow of described washings is 2m
3/ h, the pressure that washings injects is 0.5MPa, and washing time is 60min.
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.5MPa in described filtrate channel is blown, and the gas flow of described air blowing is 20m
3/ min, gas temperature is normal temperature, and gassing time is 30min.
(7) after described air blowing terminates, keep described preloading condition, by pH be 9.5 alkali lye inject the solidification treatment that described filter chamber carries out mn ion, in described solidification treatment process, in described filtrate channel, carry out stage inflation, wherein, the injection rate of alkali lye is the 15wt% of described filter cake quality, the injection pressure 0.4MPa of described alkali lye, the time of described solidification treatment is 20min; It is 9.5 that the solidification raffinate flowed out in solidification treatment process adds alkali adjustment pH, staticly settles, gets supernatant liquor and be back to as alkali lye the solidification treatment that this step carries out mn ion.
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
In this technological process, when the manganese concentration of filtrate described in described step (2) is not less than 30g/L, described filtrate enters electrolytic manganese car liquid.
Observe in above-described embodiment and comparative example and process the pattern of the manganese slag obtained and it is detected, measure wherein soluble manganese ions and NH
4 +content, result is as shown in the table,
Obviously, above-described embodiment is only for clearly example being described, and the restriction not 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 exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (8)
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 slurries;
(2) the filter chamber inner filtration that diaphragm filter press is injected in described manganese scorification slurries pressurization is obtained filter cake, filtrate returns described step (1) and washes away manganese slag as change pulp-water in order to high pressure;
(3) carry out precompressed to described filter cake, preload pressure is 0.3-0.5MPa;
(4) under preloading condition, two sections of acid are injected in described filter chamber two-stage acid leaching is carried out to described filter cake;
(5) after described two-stage acid leaching terminates, keep described preloading condition, multistage washings is injected described filter chamber and carries out multistage washing;
(6) after described washing terminates, keep described preloading condition, the gas passing into 0.3-0.4MPa in described filtrate channel is blown;
(7) after described air blowing terminates, keeping described preloading condition, is that the alkali lye of 9-10.5 injects the solidification treatment that described filter chamber carries out mn ion by pH value, in described solidification treatment process, carries out stage inflation in described filtrate channel;
(8) after solidification 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;
(9) after blowback terminates, carry out high pressure press filtration to the material in described filter chamber, press filtration terminates rear slag dumping.
2. the harmless treatment process of electrolytic manganese residues according to claim 1, is characterized 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 mn 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 raffinate flowed out in solidification treatment process adds alkali adjusted to ph, staticly settle, get supernatant liquor and be back to as alkali lye the solidification treatment that described step (7) carries out mn ion.
4. the harmless treatment process of electrolytic manganese residues according to claim 3, it is characterized in that, in described step (7), the injection rate of alkali lye is the 10-30wt% of described filter cake quality, the injection pressure of described alkali lye is than washing pressure height 0.05MPa, and the time of described solidification treatment is 5-30min.
5. according to the harmless treatment process of the arbitrary described electrolytic manganese residues of claim 1-4, it is characterized in that, in the described solidification treatment process of described step (7), stage inflation is carried out in described filtrate channel, every minor tick 10min, inflation 1min, gas temperature 30-70 DEG C, gaseous tension 0.3-0.4MPa.
6. according to the harmless treatment process of the arbitrary described electrolytic manganese residues of claim 1-5, it is characterized in that, in described step (4), the pressure that described two sections of acid are injected is 0.3-0.5MPa, described two sections of sour injection rates are the 20-150wt% of described filter cake weight, and the two-stage acid leaching time is 10-30min.
7. the harmless treatment process of electrolytic manganese residues according to claim 6, is characterized in that, in described step (5), the flow of described washings is 5-20m
3/ h, the pressure that washings injects is 0.25-0.45MPa, and washing time is 5-30min.
8., according to the harmless treatment process of the arbitrary described electrolytic manganese residues of claim 1-7, it is characterized in that, the gas flow of described air blowing is 5-20m
3/ min, gaseous tension is 0.3-0.4MPa, and gassing time is 1-5min.
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| CN108689671A (en) * | 2018-06-07 | 2018-10-23 | 广西壮族自治区环境保护科学研究院 | Manganese in electrolytic manganese residues and ammonium sulfate handle recovery method |
| CN109811148A (en) * | 2019-01-31 | 2019-05-28 | 贵州大学 | A kind of method that solvable sulfate is recycled in mangaic acid phase analysis accumulation washing |
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| CN105274580A (en) * | 2015-11-15 | 2016-01-27 | 王兆兵 | Method for comprehensively using water and manganese slag in electrolytic manganese production |
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| CN106927507A (en) * | 2017-03-29 | 2017-07-07 | 湘潭市环境保护科学研究院 | One kind electrolysis MnO2The method for preparing manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer with waste residue containing Mn in electrolysis Mn productions |
| 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 |
| CN108689671A (en) * | 2018-06-07 | 2018-10-23 | 广西壮族自治区环境保护科学研究院 | Manganese in electrolytic manganese residues and ammonium sulfate handle recovery method |
| CN109811148A (en) * | 2019-01-31 | 2019-05-28 | 贵州大学 | A kind of method that solvable sulfate is recycled in mangaic acid phase analysis accumulation washing |
| 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 |
| CN110551898A (en) * | 2019-09-16 | 2019-12-10 | 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 |
| CN116174437A (en) * | 2022-03-17 | 2023-05-30 | 铜仁筱启环保科技有限公司 | Harmless environment-friendly treatment method for electrolytic manganese slag |
| CN116174437B (en) * | 2022-03-17 | 2024-05-28 | 铜仁筱启环保科技有限公司 | Harmless environment-friendly treatment method for electrolytic manganese slag |
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