CN102241581B - Method for preparing manganese acetate from electrolytic manganese metal leaching residue - Google Patents
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Abstract
The invention discloses a method for preparing manganese acetate from electrolytic manganese metal leaching residues. The method comprises the following steps: using washing liquid of electrolytic manganese metal leaching residues as a raw material, depositing the washing liquid with carbonate and carrying out separation so as to obtain manganese carbonate deposition and deposition residual liquid; dissolving manganese carbonate deposition with sulfuric acid to obtain a manganese sulfate solution; purifying the manganese sulfate solution to obtain a high purity manganese sulfate solution and depositing the high purity manganese sulfate solution with carbonate to obtain high purity manganese carbonate; acidifying the high purity manganese carbonate with acetic acid to obtain a manganese acetate solution; precipitating SO4<2-> in the manganese acetate solution with barium acetate to obtain a pure manganese acetate solution and carrying out evaporative crystallization and drying to obtain a high purity product of manganese acetate. The method provided in the invention has the advantages of resource conservation, environment-friendliness, good economic benefits, a simple process, low investment cost, etc.
Description
Technical field
The invention belongs to hydrometallurgy and chemical production technical field, be specifically related to a kind of preparation method of manganese acetate.
Background technology
At present, the electrolytic manganese yearly capacity of China has surpassed 2,200,000 tons, and actual output 1,200,000 tons of left and right are maximum in the world electrolytic manganese production state and countries of consumption, and output in domestic accounts for more than 98% of Gross World Product.Electrolytic metal Mn is as a kind of high material-consumption, high energy consumption industry, and the rapid growth of industry has caused a large amount of consumption of resource on the one hand, and electrolytic metal Mn production has also brought very large pollution to environment on the other hand, and electrolytic manganese factory surrounding enviroment pressure is increasing.
Produce 1 ton of electrolytic manganese and approximately need 8 tons of manganese carbonate ores (Mn 15%～16%), produce waste manganese mud slag (wet slag, water ratio 25%) approximately 8 tons, the about 100g/L of solution manganous sulfate content in slag, ammonium sulfate is 110g/L approximately.To produce 1000000 tons of electrolytic metal Mns per year, annual manganous sulfate and the ammoniumsulphate soln of directly discharging from waste manganese slag reaches 2,000,000 m
3, manganous sulfate reaches 200,000 tons, and ammonium sulfate reaches 220,000 tons, and the manganese metal in its manganous sulfate and ammoniumsulphate soln and ammonia nitrogen can cause larger pollution to environment.
The catalyzer that manganese acetate is mainly produced as terephthalic acid (PTA); Also can be used as oxidation of acetaldehyde or dyeing keratin-fiber oxide catalyst, can also be as the siccative of paint, coating, print and dye mordant, fodder additives etc.Along with the develop rapidly of national economy, the consumption of manganese acetate is also increasing, and particularly in the production process of PTA, it is particularly outstanding that the application of manganese acetate seems.Therefore, exploitation high-purity acetic acid manganese product has wide development prospect.
The CN1562483A Chinese patent literature discloses a kind of novel process take the residue that contains Cobaltous diacetate, manganese acetate or liquid as raw materials recovery Cobaltous diacetate, manganese acetate catalyst, this process using hydrogen peroxide oxidation ferrous ion, the deironing of pH value is regulated in ammonification, make sorbent material with ammonium type storng-acid cation exchange resin, make the desorb desorbing agent with Spirit of Mindererus, the vacuum concentration stripping liquid obtains high purity Cobaltous diacetate, manganese acetate catalyst.
The CN1626495A Chinese patent literature discloses a kind of method for preparing manganese acetate, it is that Glacial acetic acid and electrolytic manganese are carried out building-up reactions with certain proportion, then with reacting liquid filtering clarification, concentrating under reduced pressure, crystallisation by cooling, and the crystallized product centrifuge dehydration is prepared manganese acetate.
The CN1033039A Chinese patent literature discloses a kind of take the processing method of cobalt and manganese oxide as waste Cobaltous diacetate, manganese acetate, the method is to remove to process iron ion in the cobalt manganese aqueous solution with the hydrocarbon solution of phosphoric acid ester as extraction agent, and after resolving operation, the desorbed solution saturated adsorption that backflows is made with extra care.
The CN1293260A Chinese patent literature discloses a kind of catalyst recovery technology, it is in oxidized dregs of terephthalic acid washing and adds dilute sulphuric acid to make on most of organism saturated basis of separating out, adopts storng-acid cation exchange resin to carry out cationic exchange to the aqueous solution that contains cobalt, mn ion and other trace metal ion; Before adding the strong base solution neutralization to remove iron ion, add oxygenant in solution, make the Fe in solution
2+Be converted into Fe fully
3+Thereby, iron ion is all removed in N-process.The method can make the cobalt-manganese catalyst rate of recovery be not less than 95%, and crystallizing and drying Cobaltous diacetate, the manganese acetate catalyst purity of recovery are not less than 99.7%.
the CN1226550A Chinese patent literature discloses a kind of oxide catalyst cobalt that reclaims from the residue of Production of Terephthalic Acid process, the method of manganese acetate, it comprises extraction, cationic exchange resin adsorption, the sodium-acetate desorb, concentrated, the operations such as wastewater treatment, its main points are to reach below 100ppm with sodium content in the poor sodium solution washing cobalt and manganese adsorption column of low cobalt and product post reduction finished product, satisfy the service requirements of PTA device, with the wastewater treatment post, the absorption effluent liquid is processed in addition, make the high absorption effluent liquid waste water circulation of COD value make the residue extraction agent, the waste water that the COD value is low carries out biochemical treatment, reach the purpose that reduces the catalyst recovery cost.
The 41st～43 page of the 3rd phase of " mineral products comprehensive utilization " June calendar year 2001 discloses the spent catalyst that discharges in the terephthalic acid production plant as raw material, adopt extraction-crystallization process recovery Cobaltous diacetate and manganese acetate wherein, the rate of recovery of Cobaltous diacetate and manganese acetate reaches 85%, and the Cobaltous diacetate of recovery and manganese acetate can be reused as catalyzer; The 148th～150 page of the 33rd the 3rd phase of volume of " Liaoning chemical industry " March in 2004 also discloses take manganese dirt and titanium white waste acid and prepared the method for manganese acetate as raw material, and spent acid, waste material are fully utilized.
Yet, the relevant report for preparing manganese acetate with Electrolytic Manganese Metal Residues is also disclosed in prior art.If the preparation of the processing of Electrolytic Manganese Metal Residues and manganese acetate can be organically combined, this not only to resources conservation, curb environmental pollution significant, also significant to satisfying the great demand of manganese acetate in current industry simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides a kind of resources conservation, environmental friendliness, economic benefit is high, technique is simple, cost of investment is few prepares the method for manganese acetate with the electrolysis manganese metal leaching residue.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of method for preparing manganese acetate with the electrolysis manganese metal leaching residue, comprise the following steps: take the washings of described electrolytic metal Mn leached mud as raw material, with this washings of carbonate deposition, obtain the remaining liquid of manganous carbonate precipitation and precipitation after separation; Precipitate to get manganese sulfate solution with the described manganous carbonate of sulfuric acid dissolution again; Obtain the high-purity sulphuric acid manganese solution after described manganese sulfate solution is purified, then use the described high-purity sulphuric acid manganese solution of carbonate deposition, obtain high-purity manganese carbonate; Then obtain manganese acetate solution with the described high-purity manganese carbonate of acidifying with acetic acid; At last with the SO in the described manganese acetate solution of barium acetate precipitation
4 2-Obtain pure manganese acetate solution, pure manganese acetate solution obtains high-purity acetic acid manganese product (purity reaches more than 99%) through evaporative crystallization, drying.
Above-mentioned prepares in the method for manganese acetate with the electrolysis manganese metal leaching residue, the preferred bicarbonate of ammonia of described carbonate, precipitation temperature during with described ammonium bicarbonate precipitation is preferably 5 ℃～90 ℃, sedimentation time is preferably 30min～120min, and the consumption of bicarbonate of ammonia is preferably 1.0～2.0 times of theoretical amount.
Above-mentioned prepares in the method for manganese acetate with the electrolysis manganese metal leaching residue, and the remaining liquid of described precipitation reclaims after precipitation ammonia still process and prepares ammoniacal liquor.In aforementioned precipitation ammonia still process step, can select alkali lye as precipitation agent, but the precipitation agent of preferentially selecting is calcium hydroxide.
Above-mentioned prepares in the method for manganese acetate with the electrolysis manganese metal leaching residue, and the purification process of described manganese sulfate solution preferably includes following four kinds and processes operation: utilize oxidation style to remove iron ion in manganese sulfate solution, utilize sulfurization-precipitation method to remove heavy metal ion in manganese sulfate solution, utilize the fluorination precipitation method to remove the calcium ions and magnesium ions in manganese sulfate solution and utilize concentrated flocculence to remove sila matter in manganese sulfate solution.The preferred working order of processing is for first removing iron ion, then heavy-metal ion removal, then removes the last silica removal of calcium ions and magnesium ions.
The above-mentioned method for preparing manganese acetate with the electrolysis manganese metal leaching residue, in described oxidation style, the preferred oxygenant that adopts is hydrogen peroxide, oxidizing temperature is preferably 75 ℃～90 ℃, and oxidization time is preferably 30min～120min, and the consumption of described hydrogen peroxide is preferably 2.0～6.0 times of theoretical amount.
The above-mentioned method for preparing manganese acetate with the electrolysis manganese metal leaching residue, the precipitation agent of preferably using in described sulfurization-precipitation method is Sodium dimethyldithiocarbamate 40min, the sulfide precipitation temperature is preferably 60 ℃～90 ℃, the sulfide precipitation time is preferably 30min～120min, after reaction is completed, time of repose is preferably 4h～12h, and the consumption of described Sodium dimethyldithiocarbamate 40min is preferably 30g/m
3～70g/m
3
The above-mentioned method for preparing manganese acetate with the electrolysis manganese metal leaching residue, the precipitation agent of preferably using in described fluorination precipitation method is Neutral ammonium fluoride, the fluorination precipitation temperature is preferably 70 ℃～90 ℃, the fluorination precipitation time is preferably 60min～150min, after reaction is completed, time of repose is preferably 4h～12h, and the consumption of described Neutral ammonium fluoride is preferably 1.5～4.5 times of theoretical amount.
The above-mentioned method for preparing manganese acetate with the electrolysis manganese metal leaching residue, the flocculation agent of using in described concentrated flocculence is preferably polyacrylamide (cationic flocculant), flocculation temperature is preferably 65 ℃～90 ℃, flocculation time is preferably 30min～90min, after reaction is completed, time of repose is preferably 12h～48h, and the consumption of described polyacrylamide is preferably 3g/m
3～20g/m
3
Compared with prior art, the invention has the advantages that:
1. the present invention proposes and a kind ofly produce the waste residue slag washing liquid take electrolytic metal Mn and prepare the novel process of high-purity acetic acid manganese as raw material, technique of the present invention can be prepared high-purity acetic acid manganese, and the raw material Electrolytic Manganese Metal Residues after treatment its water-soluble Mn content be down to (in butt) below 0.2%, ammonium sulfate content is down to approximately 0.22% (in butt), the comprehensive recovery of manganese is greater than 95%, and the manganese acetate quality product reaches the requirement of manganese acetate HG/T 2034-1999 quality standard;
2. in the preferred preparation technology of the present invention, also simultaneously the Waste Sulfuric Acid ammonium solution is reclaimed to prepare by product ammoniacal liquor, the comprehensive recovery of ammonium sulfate is greater than 95%, and mother liquor can be recycled.
Therefore, the high-purity acetic acid manganese that adopts preparation technology of the present invention both to develop to have extensive market outlook, reclaimed simultaneously ammonia, the difficult problem that the technique that causes can not direct motion but also the accumulation, the liquor capacity that have solved ammonium sulfate and calcium magnesium in existing Electrolytic Manganese Metal Residues washing process constantly expand.Prepare high-purity acetic acid manganese and reclaim(ed) sulfuric acid ammonium with the electrolytic manganese waste residue washings, also can effectively reduce water-soluble manganese and ammonia nitrogen pollution and the impact on environment in waste residue, have significant ecological benefits and environmental benefit, this is for energy-saving and emission-reduction and the environmental pollution improvement of electrolytic metal manganese industry, and tool is of great significance; Meanwhile, the present invention has also reclaimed the valence component that has in the electrolytic manganese waste residue, has again a great economic benefit.Step of preparation process of the present invention is simple, facility investment is few, easy handling and production cost low, application prospect is very wide.
Description of drawings
Fig. 1 is the process flow sheet of preparation manganese acetate in the embodiment of the present invention.
Embodiment
The invention will be further described below in conjunction with Figure of description and specific embodiment.
Embodiment:
A kind of method for preparing manganese acetate with the electrolysis manganese metal leaching residue of the present invention as shown in Figure 1 comprises the following steps:
1. preparation manganous carbonate: the washings of electrolytic metal Mn leached mud as raw material, after tested, contains Mn 37.82g/L in this washings in a certain electrolytic manganese process, contains (NH
4)
2SO
491.82g/L, then with this washings of ammonium bicarbonate precipitation, the bicarbonate of ammonia consumption is 1.1 times of theoretical consumption, and the temperature during precipitation is 40 ℃, the stirring sedimentation time is 30min, obtains the remaining liquid of manganous carbonate precipitation and precipitation (main liquid containing ammonium sulfate in the remaining liquid of precipitation) after filtering separation.The reaction principle of this step is:
MnSO
4+2NH
4HCO
3＝MnCO
3+(NH
4)
2SO
4+H
2O+CO
2↑。
2. sulfuric acid dissolution: the manganous carbonate that obtains with concentrated sulfuric acid dissolution step 1 again precipitates to get manganese sulfate solution; Comprise following chemical composition in this manganese sulfate solution: Mn 74.16g/L, Fe 8.93mg/L, Ca 0.584g/L, Mg 1.10g/L; The reaction principle of this step is:
MnCO
3+H
2SO
4＝MnSO
4+H
2O+CO
2↑；
As seen, reached by above two steps the purpose that manganese and magnesium separate with ammonium sulfate fully, the rate of recovery of manganese reaches 98.12%, and this will more be conducive to next step purifying.
3. the purifying of manganese sulfate solution: the manganese sulfate solution that obtains after step 2 dissolving is carried out purifying as follows;
3.1 first utilize the iron ion in oxidation style removal manganese sulfate solution: add H in manganese sulfate solution
2O
25 times of theoretical amount, temperature is controlled at 90 ℃, and the pH value is 6.5～7.0, and oxidization time is 1h, removes ferro element by this oxidation-precipitation method, and this oxidizing reaction principle is:
Fe
2+Oxidation 2Fe
2++ H
2O
2+ 2H
+=2Fe
3++ 2H
2O
Fe
3+Hydrolysis Fe
3++ 3OH
-=Fe (OH)
3↓ or Fe
3++ 3H
2O=Fe (OH)
3↓+3H
+
Make the clearance of iron reach 99% by above-mentioned oxidation-precipitation method, in the solution after deironing, the concentration of Fe is below 1mg/L, and the rate of recovery of manganese is 99.12%;
3.2 utilize the heavy metal ion in sulfurization-precipitation method removal manganese sulfate solution: add Sodium dimethyldithiocarbamate 40min (being called for short SDD) in the solution after deironing, addition is pressed 50g/m
3Meter, temperature is controlled at 60 ℃, and the sulfide precipitation churning time is 1h, and time of repose is 12h, and the reaction principle of removal heavy metal is:
Me in following formula is the heavy metals such as Cu, Co, Ni, Zn;
In solution after removing heavy metals, the content of each element is: Mn 59.75g/L, and Cu 0.47mg/L, Ni1.01mg/L, Co0.78mg/L, Pb 0.97mg/L, Zn 0.37mg/L, wherein the rate of recovery of Mn reaches 99.25%;
Remove calcium ions and magnesium ions in manganese sulfate solution 3.3 utilize the fluorination precipitation method: add again 2.5 times of NH4F theoretical amount in the solution after removal heavy metal, temperature is controlled at 90 ℃, the fluorination precipitation churning time is 2h, time of repose 12h, endpoint pH is 5.0～5.5, and the reaction principle of this step calcium-magnesium removing is:
Ca
2++2NH
4F＝CaF
2↓+2NH
4 +
Mg
2++2NH
4F＝MgF
2↓+2NH
4 +
In solution after calcium-magnesium removing, the content of each element is: Mn 74.25g/L, and Ca 1.04mg/L, Mg 13.40mg/L, the rate of recovery of manganese can reach 98.78%;
3.4 utilize the silicon ion in concentrated flocculence removal manganese sulfate solution: the solution after calcium-magnesium removing is concentrated into approximately 100g/L of Mn, then adds the flocculation agent polyacrylamide, flocculation agent consumption 6g/m
3Flocculation temperature is controlled at 75 ℃～80 ℃, the flocculation stirring time is 35min, stirring velocity 60r/min～70r/min, time of repose 24h, the flocculation silica removal is to utilize the cationic flocculant polyacrylamide to make the silicic acid polymerization in solution become macromole to form precipitation together with flocculation agent, thereby reaches the purpose of removing element silicon.Can being expressed as from collecting process of silicic acid:
In solution after silica removal, the content of each element is: Mn 96.48g/L, SiO
26.30mg/L the rate of recovery of manganese can reach 98.73%.
4. preparation high-purity manganese carbonate: the manganese sulfate solution after step 3 purifying, continuing use ammonium bicarbonate precipitation, the addition of bicarbonate of ammonia is 11 times of theoretical amount, and temperature of reaction is controlled at 40 ℃, and churning time is 30min, makes high-purity manganese carbonate after fully precipitating.
5. acidifying prepares manganese acetate solution: the high-purity manganese carbonate that step 4 is made is placed in reactor, and temperature of reaction is controlled at 102 ℃ ± 2 ℃, slowly adds aqueous acetic acid (the dense acetic acid of technical grade), and the acetic acid consumption is 2.0～2.5 times of theoretical amount, Mn in solution
2+Ionic concn is controlled at 75g/L～80g/L, and churning time is 1.5h～2h, prepares manganese acetate solution.The reaction principle of this manganese acetate preparation is: MnCO
3+ 2CH
3COOH=Mn (CH
3COO)
2+ H
2O+CO
2↑.
6. the purifying of manganese acetate solution: SO in the manganese acetate solution that makes according to step 5
4 2-Amount add barium acetate solution precipitation SO
4 2-, the addition of barium acetate is 1 times of theoretical amount, 60 ℃ of precipitation temperatures, and churning time 0.5h obtains pure manganese acetate solution after sedimentation and filtration.This purification reaction principle is: Ba (CH
3COO)
2+ SO
4 2-=BaSO
4↓+2CH
3COO
-
7. the crystallization of manganese acetate solution: the pure manganese acetate solution that step 6 makes is put into crystallization reactor, and evaporation concentration is when concentrated solution density is 1.50g/cm
3The time, stopped heating naturally cools to 40 ℃～45 ℃ of temperature under stirring, emit the manganese acetate enriched material, further crystallisation by cooling in crystallizing pan, and last centrifuge dehydration obtains the high-purity acetic acid manganese product.
The quality index of the high-purity acetic acid manganese product that the present embodiment makes is as shown in table 1 below:
Table 1: the high-purity acetic acid manganese product quality index of the present embodiment
Annotate: remove Mn (CH in table 1
3COO)
24H
2O, SO
4 2-And Cl
-Outside representing with mass percent, the unit of remainder data is ppm.
Add calcium hydroxide in liquid more than the precipitation that step 1 obtains (being mainly ammoniumsulphate soln), addition is 1.2 times of theoretical amount, boiling time 1.0h, precipitation ammonia still process, ammonia obtains ammoniacal liquor through condensation absorption tower absorption, and this ammoniacal liquor quality product meets the HG1-88-81 standard.
Prepared high-purity acetic acid manganese with the present embodiment method, and recovery obtains ammoniacal liquor, Electrolytic Manganese Metal Residues its water-soluble Mn content after treatment is down to 0.2% (in butt), ammonium sulfate content is down to 0.22% (in butt), the comprehensive recovery of manganese and ammonium sulfate is greater than 95%, and quality product reaches electronic grade acetic acid manganese quality standard.
Claims (4)
1. method for preparing manganese acetate with the electrolysis manganese metal leaching residue comprises the following steps: take the washings of described electrolytic metal Mn leached mud as raw material, with this washings of carbonate deposition, obtain the remaining liquid of manganous carbonate precipitation and precipitation after separation; Precipitate to get manganese sulfate solution with the described manganous carbonate of sulfuric acid dissolution again; Described manganese sulfate solution is purified obtains the high-purity sulphuric acid manganese solution, then uses the described high-purity sulphuric acid manganese solution of carbonate deposition, obtains high-purity manganese carbonate; Then obtain manganese acetate solution with the described high-purity manganese carbonate of acidifying with acetic acid; At last with the SO in the described manganese acetate solution of barium acetate precipitation
4 2-Obtain pure manganese acetate solution, pure manganese acetate solution obtains purity through evaporative crystallization, drying and reaches high-purity acetic acid manganese product more than 99%;
The purification process of described manganese sulfate solution comprises following processing operation: utilize oxidation style to remove iron ion in manganese sulfate solution, utilize sulfurization-precipitation method to remove heavy metal ion in manganese sulfate solution, utilize the fluorination precipitation method to remove the calcium ions and magnesium ions in manganese sulfate solution and utilize concentrated flocculence to remove sila matter in manganese sulfate solution;
The oxygenant of selecting in described oxidation style is hydrogen peroxide, and oxidizing temperature is 75 ℃～90 ℃, and oxidization time is 30min～120min, and the consumption of described hydrogen peroxide is 2.0～6.0 times of theoretical amount;
The precipitation agent of using in described sulfurization-precipitation method is Sodium dimethyldithiocarbamate 40min, the sulfide precipitation temperature is 60 ℃～90 ℃, the sulfide precipitation time is 30min～120min, standing 4h～12h after reaction is completed, and the consumption of described Sodium dimethyldithiocarbamate 40min is 30g/m
3～70g/m
3
The precipitation agent of using in described fluorination precipitation method is Neutral ammonium fluoride, and the fluorination precipitation temperature is 70 ℃～90 ℃, and the fluorination precipitation time is 60min～150min, standing 4h～12h after reaction is completed, and the consumption of described Neutral ammonium fluoride is 1.5～4.5 times of theoretical amount;
The flocculation agent of using in described concentrated flocculence is polyacrylamide, and flocculation temperature is 65 ℃～90 ℃, and flocculation time is 30min～90min, standing 12h～48h after reaction is completed, and the consumption of described polyacrylamide is 3g/m
3～20g/m
3
2. the method for preparing manganese acetate with the electrolysis manganese metal leaching residue according to claim 1, it is characterized in that: described carbonate is selected bicarbonate of ammonia, precipitation temperature during with described ammonium bicarbonate precipitation is 5 ℃～90 ℃, sedimentation time is 30min～120min, and the consumption of bicarbonate of ammonia is 1.0～2.0 times of theoretical amount.
3. the method for preparing manganese acetate with the electrolysis manganese metal leaching residue according to claim 2 is characterized in that: the remaining liquid of described precipitation reclaims after precipitation ammonia still process and prepares ammoniacal liquor.
4. the method for preparing manganese acetate with the electrolysis manganese metal leaching residue according to claim 3, it is characterized in that: the precipitation agent that described precipitation ammonia still process step is selected is calcium hydroxide.
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| CN102560156A (en) * | 2012-02-23 | 2012-07-11 | 中国恩菲工程技术有限公司 | Method for recycling manganese from P204 manganese back extraction solution in nickel laterite hydrometallurgical process |
| CN104478695B (en) * | 2014-11-26 | 2015-12-02 | 南京化学试剂有限公司 | A kind of iron ion removing technique of manganous acetate mother liquor |
| CN104496789B (en) * | 2014-12-16 | 2016-04-06 | 浙江金科过氧化物股份有限公司 | A kind of production technique applied solubleness crystallization process and prepare four water acetic acid manganese |
| CN109369375A (en) * | 2018-12-18 | 2019-02-22 | 南京化学试剂股份有限公司 | Mother liquor deferrization process during a kind of production manganese acetate |
| CN110759384A (en) * | 2019-11-08 | 2020-02-07 | 中信大锰矿业有限责任公司 | Method for preparing spheroidal manganous manganic oxide by manganese sulfate solution |
| CN111477985B (en) * | 2020-04-15 | 2023-08-15 | 中南大学 | Method for recycling waste lithium ion batteries |
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