CN108842052A - The method of comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt - Google Patents
The method of comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt Download PDFInfo
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Abstract
The invention discloses the method for comprehensive utilization of a kind of electrolytic manganese anode slag and electrolytic manganese crystallization double salt, include the following steps：(1) electrolytic manganese generated in electrolytic manganese anode slag and electrolytic manganese production process crystallization double salt is mixed, carries out low-temperature bake, obtain roasting material, and generate and contain NH3Flue gas；(2) gained roasting material is subjected to water logging, is then separated by solid-liquid separation, obtains lead smelting gas and leachate containing manganese；(3) manganese in gained leachate containing manganese is recycled using electrolysis method, or recycles the valuable metal in gained leachate containing manganese using the precipitation method.Not only process is simple for method of the invention, process conditions are mild, time-consuming short, at low cost, but also can efficiently separate Mn, Pb, Ag in electrolytic manganese anode slag, while making to crystallize Mg, Mn, NH in double salt3Separation effectively realizes electrolytic manganese anode slag and crystallizes the harmless resource processing of double salt.The method of the invention is environmentally protective, increases its economic benefit while reducing relevant enterprise environmental protection pressure.
Description
Technical field
The present invention relates to metallurgical dangerous waste, metallurgical solid waste resource reclaim process field more particularly to electrolytic manganese anode slag and electricity
The method of comprehensive utilization of Xie Meng crystallization double salt.
Background technique
China is maximum electrolytic manganese producing country, country of consumption and exported country in the world.Its manufacturer is concentrated mainly on " manganese
The ground such as triangle " (Hunan, Guizhou, Chongqing San Sheng intersection), Guangxi and Ningxia.Chinese electrolytic manganese annual output is more than 150 within 2017
Ten thousand tons.It is the industries such as stainless steel production and lithium ion battery that electrolytic manganese, which is mainly used for 200,.Since two thousand, China's electrolyzing gold
Belong to manganese industry and obtains quick development.While fast-developing, a large amount of metallurgical dangerous waste and metallurgical solid waste are generated.Electrolytic manganese sun
Pole slag belongs to the metallurgical dangerous waste in electrolytic manganese industry, and crystallization double salt belongs to the metallurgical solid waste of electrolytic manganese industry.
Electrolytic manganese anode slag is generated as the by-product in electrolytic manganese metal production process, every production 1t electrolytic manganese metal
The electrolytic manganese anode slag of 17kg~35kg, mainly with MnO2Based on, with part PbSO4、MnSO4、(NH4)2SO4、MgSO4With
And a small amount of Ag2SO4.Country's electrolytic manganese production anode plate used is based on pb-ag alloy at present, gradually with electrolytic process
Consumption, lead, silver are entered in anode slag in the form of indissoluble sulfate.Currently, electrolytic metal manganese anode slag is mainly for the production of manganese
Ferroalloy, but a large amount of exhaust gas and flue dust containing Pb are generated during processing, ambient enviroment is caused seriously to pollute, while right
The health of surrounding resident poses a serious threat.Electrolytic manganese anode slag is classified as hazardous waste by country, and manganese therein contains
Amount contains the Ag for having more than 300g/t more than 50% or more.So either from environmental protection angle or the utilization of resources
Angle, it is all extremely important for the processing of electrolytic metal manganese anode slag harmless resource.
Electrolytic manganese crystallization double salt is in electrolytic manganese production process, and one kind of generation is mainly by (NH4)2SO4、MnSO4、MgSO4、
CaSO4The composite sulfur hydrochlorate of composition.To increase Faradaic current efficiency in traditional electrolytic manganese production process, manganese sulfate need to be made to be electrolysed
Containing (the NH of 90g/L~130g/L or so in qualifying liquid4)2SO4.The a large amount of magnesite and carbonic acid of association in raw materials for production manganese spar
Calcium mineral, the calcium ions and magnesium ions in these mineral enter in leachate during acidleach with manganese ion together, the overwhelming majority
Calcium ion precipitated in the form of calcium sulfate enter slag in, remain in leachate on a small quantity.In electrolytic manganese production process, with
Leachate quiescent settling and electrolysis, leachate temperature change, (the NH in leachate4)2SO4、MnSO4、MgSO4、CaSO4
Compound crystal precipitation will occur for equal sulfate.According to statistics, every production 1t electrolytic manganese metal, the crystallization for generating 0.7t~2.5t are multiple
Salt.Wherein (NH4)2SO4Account for gross weight 80%~90%, MnSO4Account for gross weight 10%~15%, MgSO4Account for gross weight 3%~
5%, CaSO4Account for the 0.5%~1% of gross weight.Crystallize double salt (NH therein4)2SO4、MnSO4、MgSO4It is solubility salt,
If untreated stockpiling, surrounding aqueous environment will be caused to pollute with rain drop erosion.Wherein contain part of sulfuric acid manganese, tool simultaneously
There is important recovery value.Therefore, from environmental protection angle and utilization of resources angle, crystallization double salt requires to carry out effective and reasonable
Processing.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, a kind of electrolytic manganese anode slag and electrolysis are provided
The method of comprehensive utilization of manganese crystallization, not only process is simple for method of the invention, process conditions are mild, the time required to process it is short, at
This is low, and can efficiently separate Mn, Pb, Ag in electrolytic manganese anode slag, while making to crystallize Mg, Mn, NH in double salt3Point
From the effectively harmless resource processing of realization electrolytic manganese anode slag and crystallization double salt.The method of the invention is environmentally protective, reduces phase
Its economic benefit is increased while closing environmental protection of enterprise pressure.
In order to solve the above technical problems, the present invention uses following technical scheme：
The method of comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt, includes the following steps：
(1) electrolytic manganese generated in electrolytic manganese anode slag and electrolytic manganese production process crystallization double salt is mixed, carries out low temperature
Roasting obtains roasting material, and generates and contain NH3Flue gas；
(2) gained roasting material is subjected to water logging, is then separated by solid-liquid separation, obtains lead smelting gas and leachate containing manganese；
(3) manganese in gained leachate containing manganese is recycled using electrolysis method, or recycles gained leachate containing manganese using the precipitation method
In valuable metal.
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that the step (1)
In, according to mass ratio meter, (electrolytic manganese anode slag) ︰ m (electrolytic manganese crystallization double salt) is 1 ︰, 2~1 ︰ 6 to m.
And/or in the step (1), the temperature of the low-temperature bake is 400 DEG C~650 DEG C；The low-temperature bake when
Between be 30min~180min.
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that further including will be described
Step (1) generates described containing NH3Off-gas recovery；The method of the recycling is：Contain NH to described with sulfuric acid solution3Flue gas carries out
It absorbs, obtains ammonium sulfate product；Or contain NH to described with water3Flue gas is absorbed, and ammonium hydroxide product is obtained.
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that the step (2)
In, the liquid-solid ratio of the water logging is 5 ︰ of ︰ 1mL/g~2 1mL/g；The temperature of the water logging is 25 DEG C~60 DEG C；The water logging when
Between be 20min~60min.
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that further include by step
(2) resulting lead smelting gas is unified stores up, and sells to Qian Yin manufacturing enterprise or individually recycling lead silver resource as lead, silver material.
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that the step (3)
In, when recycling the valuable metal in gained leachate containing manganese using the precipitation method, include the following steps：Into gained leachate containing manganese
The first precipitating reagent precipitating manganese is added, is separated by solid-liquid separation after the completion of to be precipitated, obtains containing manganese product and the first filtrate, to gained the
The second precipitating reagent precipitating magnesium is added in one filtrate, is separated by solid-liquid separation, is obtained containing magnesium products and the second filtrate after the completion of to be precipitated.
Mg in the technical program, when using the first precipitating reagent precipitating manganese, in leachate containing manganese2+Into the first filtrate.
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that first precipitating
Agent is CO2With NH3Mixed gas, ammonium carbonate, at least one of ammonium hydrogen carbonate, described containing manganese product is manganese carbonate；It is described heavy
The reaction temperature of shallow lake manganese is 25 DEG C~80 DEG C；The reaction time of the precipitating manganese is 30min~180min；When first precipitating
Agent is CO2With NH3Mixed gas when, precipitate manganese when solution pH value range be 4.5~8.9；
And/or second precipitating reagent be at least one of oxalic acid, ammonium oxalate, ammonium binoxalate, it is described to be containing magnesium products
Magnesium oxalate；The reaction temperature of the precipitating magnesium is 25 DEG C~60 DEG C；The reaction time of the precipitating magnesium is 30min~120min.
In the technical program, when using ammonium carbonate and/or ammonium hydrogen carbonate as the first precipitating reagent, do not need to adjust during precipitating manganese
pH。
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that first precipitating
Agent is ammonia or ammonium hydroxide, and the manganese product that contains is Mn (OH)2；The reaction temperature of the precipitating manganese is 25 DEG C~50 DEG C；It is described heavy
The pH value of shallow lake manganese is 7.4~8.9；
And/or second precipitating reagent is any one in oxalic acid, ammonium oxalate, ammonium binoxalate, ammonia and ammonium hydroxide, institute
Stating containing magnesium products is magnesium oxalate or Mg (OH)2；The reaction temperature of the precipitating magnesium is 25 DEG C~60 DEG C.
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that further including will be described
The pH value of second filtrate is adjusted to no more than 7.3, is then returned in the step (2), is used as the leaching agent of the water logging.
The method of comprehensive utilization of above-mentioned electrolytic manganese anode slag and electrolytic manganese crystallization double salt, it is preferable that the step (3)
In, when recycling the manganese in gained leachate containing manganese using electrolysis method, include the following steps：Gained leachate containing manganese is used for subsequent
Electrolysis production manganese metal or manganese dioxide.
The present invention is mixed by the way that electrolytic manganese anode slag and electrolytic manganese are crystallized double salt, carries out low-temperature bake, then will be resulting
Low-temperature bake material carries out water logging, isolates lead smelting gas, while recycling manganese element therein, reaches the innoxious of electrolytic manganese anode slag
The purpose of processing.In addition, also containing NH for what low-temperature bake generated3Flue gas is for producing ammonium sulfate or ammonium hydroxide.In the present invention, lead to
Multistep innovation is crossed, so that the rate of recovery of manganese element is high, electrolytic manganese anode slag, crystallization double salt realize innoxious, recycling treatment.
Compared with the prior art, the advantages of the present invention are as follows：
(1) present invention is by largely studying, innovatively propose a kind of simple process, process conditions be mild, needed for process
Time is short, the method at low cost to electrolytic manganese anode slag and electrolytic manganese crystallization double salt integrated treatment, and this method not only realizes
To electrolytic manganese anode slag, the harmless treatment of double salt is crystallized, while effectively having recycled manganese therein, ammonium, magnesium resource, so not only
It reduces electrolytic manganese anode slag and crystallizes the environmental protection pressure of double salt stockpiling, while realizing the recycling of manganese, ammonium, magnesium resource.
It is (2) innovatively that electrolytic manganese anode slag and electrolytic manganese crystallization both waste materials of double salt is baking mixed in the present invention,
In roasting process, Mn element is reduced, then obtained roasting material is carried out water logging, so that lead and silver enter lead smelting gas, Mg and Mn
Respectively with Mg2+And Mn2+Into leachate containing manganese, entire leaching process is without consuming soda acid.Obtaining lead smelting gas can be used as Ag and Pb
The raw material of recycling；Obtained leachate containing manganese can be used for subsequent electrolytic manganese metal or electrolytic manganese dioxide production, can also use
The precipitation method recycle manganese and magnesium therein, realize the complete utilization to anode slag.
(3) in the present invention, contain NH for what electrolytic manganese anode slag and electrolytic manganese crystallization double salt low-temperature bake generated3Flue gas is used
In production ammonium sulfate product or ammonium hydroxide product, it is not only effectively utilized exhaust gas, but also prevent from polluting the environment.
(4) it in the present invention, by the way that the filtrate obtained after the heavy manganese of manganese leachate, magnesium sinking will be contained back to water logging process, realizes
Water resource is recycled, and reduces discharge of wastewater.
(5) entire process flow of the invention compared with short, energy consumption is small, it is time-consuming less, it is at low cost, pollution it is small, and promoter manganese return
High income.
Detailed description of the invention
Fig. 1 is the work of the electrolytic manganese anode slag of the embodiment of the present invention 1,2 and the method for comprehensive utilization of electrolytic manganese crystallization double salt
Skill flow diagram.
Fig. 2 is the technique of the electrolytic manganese anode slag of the embodiment of the present invention 3 and the method for comprehensive utilization of electrolytic manganese crystallization double salt
Flow diagram.
Fig. 3 is the technique of the electrolytic manganese anode slag of the embodiment of the present invention 4 and the method for comprehensive utilization of electrolytic manganese crystallization double salt
Flow diagram.
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
Electrolytic manganese anode slag and electrolytic manganese crystallization double salt in following embodiment are taken from common electrolytic manganese residues factory.Its
In, electrolytic manganese anode slag is as the by-product in electrolytic manganese metal production process, mainly with MnO2Based on, with part
PbSO4、MnSO4、(NH4)2SO4、MgSO4And a small amount of Ag2SO4；Electrolytic manganese crystallization double salt is produced in electrolytic manganese production process
Raw one kind mainly includes (NH4)2SO4、MnSO4、MgSO4And CaSO4Composite sulfur hydrochlorate.
Embodiment 1
A kind of utilization method of electrolytic manganese anode slag and electrolytic manganese crystallization double salt, process flow diagram is as shown in Figure 1, packet
Include following steps：
(1) the electrolytic manganese anode slag that is taken slag factory, electrolytic manganese crystallization double salt drying, will be dried with powder machine or crusher
Electrolytic manganese anode slag afterwards, crystallization double salt are crushed to 100 mesh hereinafter, ((electrolytic manganese crystallizes multiple electrolytic manganese anode slag) ︰ m according to m
Salt) be 1 ︰ 3 uniformly mixing, using rotary kiln at 550 DEG C low-temperature bake 120min, obtain roasting material, and generate and contain NH3Cigarette
Gas is absorbed using sulfuric acid solution and contains NH3Flue gas, obtains ammonium sulfate, and heating evaporation crystallization obtains ammonium sulfate product.
(2) the resulting roasting material of step (1) and water are sized mixing according to 3 ︰ 1mL/g of liquid-solid ratio, then by gained slurry
It is placed in 40 DEG C of stirred in water bath water logging, reacts 30min, filters pressing is then carried out and obtains Pb, Ag slag and leachate containing manganese, wherein electricity
Xie Meng crystallizes Mn, Mg in double salt respectively with Mn2+、Mg2+Into in leachate containing manganese, Mn, Mg of electrolytic manganese anode slag respectively with
Mn2+、Mg2+Into in leachate containing manganese.
(3) by CO2With contain NH3Flue gas is passed into step (2) resulting leachate containing manganese and carries out precipitating manganese, in 50 DEG C of items
2h is reacted under part, obtains liquid after manganese carbonate and heavy manganese, electrolytic manganese anode in entire technical process to after the reaction was completed, carry out filters pressing
The comprehensive recovery of manganese is 97.5% in slag and crystallization double salt.In this step, it need to be passed through into leachate containing manganese containing NH3Flue gas,
So that magnesium is not deposited, efficiently separated with manganese, contains NH when precipitating manganese3The pH value range that the intake of flue gas meets solution is
4.5~8.9, wherein containing NH3Flue gas can elder generation and CO2It is passed through again after mixing, it can not also be with CO2Mixing is passed directly into.
(4) oxalic acid solution is added to obtained by step (3) to liquid after sinking manganese and 2h is reacted, to fully reacting under the conditions of 60 DEG C
Afterwards, it carries out filters pressing and obtains magnesium oxalate and filtrate, filtrate returns to water logging process, recycles.
In the present embodiment, what is generated in step (1) contains NH3Flue gas can also be absorbed with water, obtain ammonium hydroxide product, or use it
He can be absorbed using containing NH3NH in flue gas3Absorption of Medium.
CO in the present embodiment, in step (3)2Contain NH with a small amount of3Flue gas can also be used ammonium carbonate or ammonium hydrogen carbonate etc. and replace
Generation.
In the present embodiment, the substitution such as ammonium oxalate, ammonium binoxalate is can also be used in the oxalic acid in step (4), but after precipitating magnesium,
The pH value of obtained filtrate need to be detected, when pH value be not more than 7.3, preferably 4.5~7.3, directly gained filtrate can be returned
The water logging process returned in step (2) is used as leaching agent, when pH value is greater than 7.3, then need for the pH value of filtrate to be adjusted to no more than 7.3 with
Afterwards, can the water logging process of return step (2) be used as leaching agent.
Embodiment 2
A kind of utilization method of electrolytic manganese anode slag and electrolytic manganese crystallization double salt, process flow diagram is as shown in Figure 1, packet
Include following steps：
(1) the electrolytic manganese anode slag that is taken slag factory, electrolytic manganese crystallization double salt drying, will be dried with powder machine or crusher
Electrolytic manganese anode slag afterwards, electrolytic manganese crystallization double salt are crushed to 100 mesh hereinafter, according to m (electrolytic manganese anode slag) ︰ m (electrolytic manganese knot
Brilliant double salt) be 1 ︰ 2.5 uniformly mixing, using rotary kiln at 600 DEG C low-temperature bake 90min, obtain roasting material, and generate and contain
NH3Flue gas is absorbed using pure water and contains NH3Flue gas obtains ammonium hydroxide product.
(2) the resulting roasting material of step (1) and water are sized mixing according to 5 ︰ 1mL/g of liquid-solid ratio, then by gained slurry
It is placed in 50 DEG C of stirred in water bath water logging, reacts 60min, filters pressing is then carried out and obtains Pb, Ag slag and filtrate containing manganese, wherein being electrolysed
Manganese crystallizes Mn, Mg in double salt respectively with Mn2+、Mg2+Into in leachate containing manganese, Mn, Mg of electrolytic manganese anode slag are respectively with Mn2 +、Mg2+Into in leachate containing manganese.
(3) by CO2With contain NH3Flue gas is passed into step (2) resulting leachate containing manganese and carries out precipitating manganese, in 60 DEG C of items
3h is reacted under part, obtains liquid after manganese carbonate and heavy manganese, electrolytic manganese anode in entire technical process to after the reaction was completed, carry out filters pressing
The comprehensive recovery of manganese is 96.8% in slag and crystallization double salt.In this step, it need to be passed through into leachate containing manganese containing NH3Flue gas,
So that magnesium is not deposited, efficiently separated with manganese, contains NH when precipitating manganese3The pH value range that the intake of flue gas meets solution is
4.5~8.9, wherein containing NH3Flue gas can elder generation and CO2It is passed through again after mixing, it can not also be with CO2Mixing is passed directly into.
(4) oxalic acid solution is added to obtained by step (3) to liquid after sinking manganese and 2h is reacted, to fully reacting under the conditions of 50 DEG C
Afterwards, it carries out filters pressing and obtains magnesium oxalate and filtrate, filtrate returns to water logging process, recycles.
Precipitating reagent CO in the present embodiment, in step (3)2With contain NH3The substitution such as ammonium carbonate, ammonium hydrogen carbonate can be used in flue gas.
In the present embodiment, the substitution such as ammonium oxalate, ammonium binoxalate is can also be used in the oxalic acid in step (4), but after precipitating magnesium,
The pH value of obtained filtrate need to be detected, when pH value be not more than 7.3, preferably 4.5~7.3, directly gained filtrate can be returned
The water logging process returned in step (2) is used as leaching agent, when pH value is greater than 7.3, then need for the pH value of filtrate to be adjusted to no more than 7.3 with
Afterwards, can the water logging process of return step (2) be used as leaching agent.
Embodiment 3
A kind of utilization method of electrolytic manganese anode slag and electrolytic manganese crystallization double salt, process flow diagram is as shown in Fig. 2, packet
Include following steps：
(1) the electrolytic manganese anode slag that is taken slag factory, electrolytic manganese crystallization double salt drying, will be dried with powder machine or crusher
Electrolytic manganese anode slag afterwards, crystallization double salt are crushed to 100 mesh hereinafter, ((electrolytic manganese crystallizes multiple electrolytic manganese anode slag) ︰ m according to m
Salt) be 1 ︰ 3 uniformly mixing, using rotary kiln at 550 DEG C low-temperature bake 120min, obtain roasting material, and generate and contain NH3Cigarette
Gas is absorbed using sulfuric acid solution and contains NH3Flue gas, obtains ammonium sulfate, and heating evaporation crystallization obtains ammonium sulfate product.
(2) the resulting roasting material of step (1) and water are sized mixing according to 3 ︰ 1mL/g of liquid-solid ratio, then by gained slurry
It is placed in 40 DEG C of stirred in water bath water logging, reacts 30min, filters pressing is then carried out and obtains Pb, Ag slag and leachate containing manganese, wherein electricity
Xie Meng crystallizes Mn, Mg in double salt respectively with Mn2+、Mg2+Into in leachate containing manganese, Mn, Mg of electrolytic manganese anode slag respectively with
Mn2+、Mg2+Into in leachate containing manganese.
(3) NH will be contained3Flue gas, which is passed into step (2) resulting leachate containing manganese, adjusts pH value to 7.4~8.9, carries out
Manganese is precipitated, reacts 2h under the conditions of 50 DEG C, obtains Mn (OH) to after the reaction was completed, carry out filters pressing2With liquid after heavy manganese.
(4) oxalic acid solution is added to obtained by step (4) after sinking manganese in liquid, under the conditions of 60 DEG C, 2h is reacted, wait react
Filters pressing is carried out after complete, obtains magnesium oxalate and filtrate, the water logging process of gained filtrate return step (2) is used as leaching agent.This step
In rapid, using oxalic acid solution as precipitating reagent, the oxalic acid solution of this step can also be used ammonium hydroxide or containing NH3Flue gas substitution, when with
Ammonium hydroxide contains NH3When flue gas is as precipitating reagent, carry out precipitation reaction, when precipitating after heavy manganese the pH value of liquid not less than 9, preferably 9~
11, after complete reaction, carries out filters pressing and obtain Mg (OH)2And filtrate, then the pH value of resulting filtrate need to be brought to and be not more than
7.3, preferably 4.5~7.3, the water logging process of filtrate return step (2) can be used as leaching agent.
In the present embodiment, what is generated in step (1) contains NH3Flue gas can also be absorbed with water, obtain ammonium hydroxide product, or use it
He can be absorbed using containing NH3NH in flue gas3Absorption of Medium.
In the present embodiment, contain NH in step (3)3Ammonium hydroxide substitution can be used in flue gas.
In the present embodiment, ammonium oxalate or ammonium binoxalate substitution is can be used in the oxalic acid solution in step (4), need to filter to obtaining
The pH value of liquid is detected, can directly will be in gained filtrate return step (2) when pH value is not more than 7.3, preferably 4.5~7.3
Water logging process is used as leaching agent, when pH value is greater than 7.3, then after needing for the pH value of filtrate to be adjusted to no more than 7.3, can return to step
Suddenly the water logging process of (2) is used as leaching agent.
Embodiment 4
A kind of method of comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt, process flow diagram such as Fig. 3 institute
Show, includes the following steps：
(1) the electrolytic manganese anode slag that is taken slag factory, crystallization double salt drying, the electrolytic manganese anode slag, crystallization after drying are multiple
Salt powder machine or crusher are crushed to 100 mesh hereinafter, (electrolytic manganese anode slag) ︰ m (electrolytic manganese crystallization double salt) is 1 ︰ according to m
2.5 uniformly mixing, using rotary kiln at 600 DEG C low-temperature bake 90min, obtain roasting material, and generate and contain NH3Flue gas uses
Pure water, which absorbs, contains NH3Flue gas obtains ammonium hydroxide product.
(2) the resulting roasting material of step (1) and water are sized mixing according to 5 ︰ 1mL/g of liquid-solid ratio, then by gained slurry
It is placed in 50 DEG C of stirred in water bath water logging, reacts 60min, filters pressing is then carried out and obtains Pb, Ag slag and leachate containing manganese, wherein electricity
Xie Meng crystallizes Mn, Mg in double salt respectively with Mn2+、Mg2+Into in leachate containing manganese, Mn, Mg of electrolytic manganese anode slag respectively with
Mn2+、Mg2+Into in leachate containing manganese.
(3) resulting leachate containing manganese is sent to the workshop of electrolysis production manganese metal or manganese dioxide, Pb, the Ag that will be obtained
Slag is unified to be stored up, and sells to Qian Yin manufacturing enterprise or individually recycling lead silver resource with lead, silver material.
Although the present invention is disclosed as above with preferred embodiment, however, it is not intended to limit the invention.It is any to be familiar with ability
The technical staff in domain, without deviating from the scope of the technical scheme of the present invention, all using the technology contents pair of the disclosure above
Technical solution of the present invention makes many possible changes and modifications or equivalent example modified to equivalent change.Therefore, all
Without departing from the content of technical solution of the present invention, according to the present invention technical spirit any simple modification made to the above embodiment,
Equivalent variations and modification, all shall fall within the protection scope of the technical scheme of the invention.
Claims (10)
1. the method for comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt, which is characterized in that include the following steps：
(1) electrolytic manganese generated in electrolytic manganese anode slag and electrolytic manganese production process crystallization double salt is mixed, carries out low-temperature bake,
Roasting material is obtained, and generates and contains NH3Flue gas；
(2) gained roasting material is subjected to water logging, is then separated by solid-liquid separation, obtains lead smelting gas and leachate containing manganese；
(3) manganese in gained leachate containing manganese is recycled using electrolysis method, or is recycled in gained leachate containing manganese using the precipitation method
Valuable metal.
2. the method for comprehensive utilization of electrolytic manganese anode slag according to claim 1 and electrolytic manganese crystallization double salt, feature exist
In in the step (1), according to mass ratio meter, (electrolytic manganese anode slag) ︰ m (electrolytic manganese crystallization double salt) is 1 ︰, 2~1 ︰ 6 to m.
And/or in the step (1), the temperature of the low-temperature bake is 400 DEG C~650 DEG C；The time of the low-temperature bake is
30min~180min.
3. the method for comprehensive utilization of electrolytic manganese anode slag according to claim 1 and electrolytic manganese crystallization double salt, feature exist
In, further include the step (1) is generated it is described containing NH3Off-gas recovery；The method of the recycling is：With sulfuric acid solution to institute
It states containing NH3Flue gas is absorbed, and ammonium sulfate product is obtained；Or contain NH to described with water3Flue gas is absorbed, and ammonium hydroxide product is obtained.
4. the method for comprehensive utilization of electrolytic manganese anode slag according to claim 1 and electrolytic manganese crystallization double salt, feature exist
In in the step (2), the liquid-solid ratio of the water logging is 5 ︰ of ︰ 1mL/g~2 1mL/g；The temperature of the water logging is 25 DEG C~60
℃；The time of the water logging is 20min~60min.
5. the method for comprehensive utilization of electrolytic manganese anode slag according to claim 1 and electrolytic manganese crystallization double salt, feature exist
In further including storing up the resulting lead smelting gas of step (2) is unified, sell to Qian Yin manufacturing enterprise as lead, silver material or individually return
Receive lead silver resource.
6. the comprehensive utilization side of electrolytic manganese anode slag according to any one of claims 1 to 5 and electrolytic manganese crystallization double salt
Method, which is characterized in that in the step (3), when recycling the valuable metal in gained leachate containing manganese using the precipitation method, including such as
Lower step：The first precipitating reagent precipitating manganese is added into gained leachate containing manganese, is separated by solid-liquid separation, is contained after the completion of to be precipitated
The second precipitating reagent precipitating magnesium is added into the first filtrate of gained, carries out solid-liquid point after the completion of to be precipitated for manganese product and the first filtrate
From obtaining containing magnesium products and the second filtrate.
7. the method for comprehensive utilization of electrolytic manganese anode slag according to claim 6 and electrolytic manganese crystallization double salt, feature exist
In first precipitating reagent is CO2With NH3Mixed gas, ammonium carbonate, at least one of ammonium hydrogen carbonate, it is described to contain manganese product
For manganese carbonate；The reaction temperature of the precipitating manganese is 25 DEG C~80 DEG C；It is described precipitating manganese reaction time be 30min~
180min；When first precipitating reagent is CO2With NH3Mixed gas when, precipitate manganese when solution pH value range be 4.5~
8.9；
And/or second precipitating reagent is at least one of oxalic acid, ammonium oxalate, ammonium binoxalate, the magnesium products that contain are oxalic acid
Magnesium；The reaction temperature of the precipitating magnesium is 25 DEG C~60 DEG C；The reaction time of the precipitating magnesium is 30min~120min.
8. the method for comprehensive utilization of electrolytic manganese anode slag according to claim 6 and electrolytic manganese crystallization double salt, feature exist
In first precipitating reagent is ammonia or ammonium hydroxide, and the manganese product that contains is Mn (OH)2；The reaction temperature of the precipitating manganese is 25
DEG C~50 DEG C；The pH value of the precipitating manganese is 7.4~8.9；
And/or second precipitating reagent is any one in oxalic acid, ammonium oxalate, ammonium binoxalate, ammonia and ammonium hydroxide, it is described to contain
Magnesium products are magnesium oxalate or Mg (OH)2；The reaction temperature of the precipitating magnesium is 25 DEG C~60 DEG C.
9. the method for comprehensive utilization of electrolytic manganese anode slag according to claim 6 and electrolytic manganese crystallization double salt, feature exist
In further including that the pH value of second filtrate is adjusted to no more than 7.3, then return in the step (2), be used as the water
The leaching agent of leaching.
10. the comprehensive utilization side of described in any item electrolytic manganese anode slags and electrolytic manganese crystallization double salt according to claim 1~5
Method, which is characterized in that in the step (3), when recycling the manganese in gained leachate containing manganese using electrolysis method, including walk as follows
Suddenly：Gained leachate containing manganese is used for subsequent electrolysis production manganese metal or manganese dioxide.
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