CN101585554B - Method for preparing manganous carbonate by using waste slag and waste water containing manganese as raw materials - Google Patents
Method for preparing manganous carbonate by using waste slag and waste water containing manganese as raw materials Download PDFInfo
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- CN101585554B CN101585554B CN2009100408630A CN200910040863A CN101585554B CN 101585554 B CN101585554 B CN 101585554B CN 2009100408630 A CN2009100408630 A CN 2009100408630A CN 200910040863 A CN200910040863 A CN 200910040863A CN 101585554 B CN101585554 B CN 101585554B
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Abstract
The invention discloses a method for preparing manganous carbonate by using waste slag and waste water containing manganese as raw materials, which is carried out as follows: reducing manganese dioxide by oxalic acid; oxidizing the ferrous iron therein into ferric iron by peroxide to form hydroxid deposit; neutralizing sulphuric acid therein by ammonia; depositing and removing heavy metal ions by ammonium sulfide; condensing to obtain ammonium manganous sulfate crystallization; reacting the ammonium manganous sulphate with ammonium hydrogen carbonate to prepare the manganous carbonate and obtain ammonium sulphate; the invention makes full use of reaction waste material and transforms water materials into useful elements; meanwhile, the invention can reduce emission and environmental pollution, which provides an efficient method for disposing waste slag and waste water containing manganese.
Description
Technical field
The present invention relates to chemical field, particularly a kind of to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate.
Background technology
In the production process of aubepine; with natural manganese dioxide (pyrolusite) is oxygenant; usually can produce a large amount of manganese waste slag and waste water of containing, wherein contain the Manganse Dioxide that manganese waste slag contains 20～40% quality, Mn-bearing waste water contains sulfuric acid about 10% quality and the bivalent manganese of 50～60g/L.According to estimates, a factory that produces 100 tons of aubepines per year, in the annual waste residue and waste water that produces, manganese content is up to 160 tons.If these contain manganese waste slag and waste water not treated just direct discharging, valuable Mineral resources have not only greatly been wasted, also with serious environment pollution.In the production of Resorcinol, also adopt similar technology, can produce equally and contain manganese waste slag and waste water in a large number, need deal carefully with and recycle.Therefore, recycling contains manganese waste slag and waste water, not only can obtain remarkable economic efficiency, and to reducing environmental pollution, making full use of Mineral resources has very positive meaning.
The range of application of manganous carbonate is very extensive, can be used to produce used in electronic industry soft magnetic ferrite, mangal and manganese-silicon, fertilizer and fodder additives, enamel pigment, varnish catalyzer etc.Manganous carbonate is that raw material is produced with electrolytic manganese or manganous sulfate, bicarbonate of ammonia etc. generally.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of utilization of waste material is provided, reduces pollution and discharging, environmental friendliness, cost are low, technology is simply to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate.
Purpose of the present invention is achieved through the following technical solutions:
A kind of to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, comprise the steps:
(1) Mn-bearing waste water of 1000 mass parts and the manganese waste slag that contains of 50 mass parts are put into reactor, stir the oxalic acid that adds 15～32 mass parts down, reacted 15～30 minutes down, filter then and obtain filtrate at 75～90 ℃;
(2) (massfraction is 30% to add the superoxol of 5～10 mass parts in the filtrate that step 1 obtains, be quality that peroxide is crossed hydrogen account for the superoxol total mass 30%), the pH value that the ammonia soln (massfraction is 25%) that adds 110～125 mass parts simultaneously is neutralized to reaction system is 5.0～7.0; Reacted 25～35 minutes down at 30～60 ℃, filter and obtain filtrate;
(3) filtrate that step 2 is obtained is heated to 55～65 ℃, adds the ammonium sulfide solution (massfraction is 5%) of 3～5 mass parts, and the pH value that keeps reaction system simultaneously is 6.0～6.5, reacts 2 hours down at 60～65 ℃, filters and obtains filtrate;
(4) in the filtrate that step 3 obtains, add the ammonium sulfate of 30～60 mass parts, be heated to solid and dissolve fully, concentrate, crystallization, obtain the ammonium manganous sulfate crystal;
(5) with the ammonium manganous sulfate crystal with water dissolution after, join massfraction and be in 5～20% the ammonium bicarbonate soln, stirred 25～35 minutes down at 10～60 ℃, obtain filter cake and filtrate after the filtration respectively; Filtrate concentrating obtains ammonium sulfate, washes filter cake with water and dry to obtain manganous carbonate.
In the step 1, describedly contain the Manganse Dioxide that manganese waste slag contains 20～40% quality, Mn-bearing waste water contains sulfuric acid about 10% quality and the bivalent manganese of 50～60g/L.
In the step 1, consumption of oxalic acid is preferably 20～28 mass parts, more preferably 24 mass parts; Temperature is preferably 80 ℃; Time is preferably 20 minutes.
In the step 2, described hydrogen peroxide consumption is preferably 5 mass parts; Ammonia volume is preferably 110～120 mass parts, more preferably 115 mass parts; The pH value is preferably 5.0～6.0, and more preferably 5.5; Temperature is preferably 40 ℃.
In the step 3, described ammonium sulfide consumption is preferably 4 mass parts; Temperature is preferably 60 ℃.
In the step 4, described ammonium sulfate consumption is preferably 30～40 mass parts, more preferably 34 mass parts.
In the step 5, the mass ratio of ammonium manganous sulfate and water is 1: 2～10, is preferably 1: 4; The mol ratio of ammonium manganous sulfate and bicarbonate of ammonia is 1: 2～4, is preferably 1: 2; The massfraction of ammonium bicarbonate soln is preferably 10%.
In the step 5, temperature of reaction is preferably 25 ℃; Described filter cake, is dried down at 70～80 ℃ then and is obtained manganous carbonate more than 3 times with 20～50 ℃ of water washings; The temperature of washing water is preferably 40 ℃.
Adding hydrogen peroxide in step 2 can be the Fe in the filtrate
2+Be oxidized to Fe
3+, the pH value of reaction system is controlled at 5.0～7.0, both made Fe
3+, Al
3+The formation precipitation of hydroxide is complete, can prevent Mn again
2+Form Mn (OH)
2Precipitation.In step 3, add ammonium sulfide and can make the heavy metal ion in the waste water and dregs form sulfide and precipitate and separate, the pH value of reaction system is controlled at 6.0～6.5, can prevent Mn
2+Form the MnS precipitation.
The present invention compared with prior art has following advantage and effect:
(1) the present invention fully recycle produce in the chemical process contain the manganese waste slag waste water resource, turn waste into wealth, reduced discharging and environmental pollution.
(2) the invention from the Mn-bearing waste water waste residue, prepare highly purified ammonium manganous sulfate, and further obtain manganous carbonate, technological process is easy, good product quality, cost is low, rate of recovery height.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
With the Manganse Dioxide oxidation style prepare aubepine contain manganese waste slag (about 50 gram) and waste water (about 1000 grams) is put into reactor, heating is stirred and is slowly added 24 gram oxalic acid down, in 80 ℃ of reactions 30 minutes down, filtration.It is 30% superoxol that filtrate adds 5 gram mass marks, and heating adds 115 gram mass marks and be 25% ammonia soln simultaneously, regulates pH ≈ 5.5,40 ℃ of reactions 30 minutes down, filters.Filtrate is heated to 60 ℃, adds 5 gram mass marks and be 5% ammonium sulfide solution, regulates 6.0,60 ℃ of reactions of pH ≈ 2 hours, filters.Add 34 gram ammonium sulfate solids in filtrate, after the heating for dissolving, concentrated, crystallization obtain ammonium manganous sulfate crystal 3 50 grams.The rate of recovery of bivalent manganese is 79.5%.
Embodiment 2
With the Manganse Dioxide oxidation style prepare aubepine contain manganese waste slag (about 50 gram) and waste water (about 1000 grams) is put into reactor, heating is stirred and is slowly added 32 gram oxalic acid down, in 75 ℃ of reactions 30 minutes down, filtration.It is 30% superoxol that filtrate adds 10 gram mass marks, and heating adds 125 gram mass marks and be 25% ammonia soln simultaneously, regulates pH ≈ 6.0,50 ℃ of reactions 30 minutes down, filters.Filtrate is heated to 60 ℃, adds 4 gram mass marks and be 5% ammonium sulfide solution, regulates 6.5,65 ℃ of reactions of pH ≈ 2 hours, filters.Add 60 gram ammonium sulfate solids in filtrate, after the heating for dissolving, concentrated, crystallization obtain ammonium manganous sulfate crystal 3 43 grams.The rate of recovery of bivalent manganese is 77.9%.
Embodiment 3
With the Manganse Dioxide oxidation style prepare aubepine contain manganese waste slag (about 50 gram) and waste water (about 1000 grams) is put into reactor, heating is stirred and is slowly added 20 gram oxalic acid down, in 90 ℃ of reactions 15 minutes down, filtration.It is 30% superoxol that filtrate adds 5 gram mass marks, and heating adds 116 gram mass marks and be 25% ammonia soln simultaneously, regulates pH ≈ 5.5,40 ℃ of reactions 30 minutes down, filters.Filtrate is heated to 60 ℃, adds 5 gram mass marks and be 5% ammonium sulfide solution, regulates 6.0,60 ℃ of reactions of pH ≈ 2 hours, filters.Add 34 gram ammonium sulfate solids in filtrate, after the heating for dissolving, concentrated, crystallization obtain ammonium manganous sulfate crystal 3 40 grams.The rate of recovery of bivalent manganese is 77.2%.
Embodiment 4
Get ammonium manganous sulfate crystal 3 9.1 grams, after 200 gram water dissolution, under 40 ℃, be added drop-wise in the solution that is made into by 15.8 gram bicarbonate of ammonia and 300 gram water, drip off and stirred 30 minutes, filter.Filter cake is with 40 ℃ water washing 3 times, after the 70-80 ℃ of oven dry manganous carbonate 11.0 grams; Filtrate is concentrated into dried ammonium sulfate 25.8 grams that obtain.
Embodiment 5
Get ammonium manganous sulfate crystal 6 0.0 gram, after 200 gram water dissolution, under 25 ℃, be added drop-wise in the solution that is made into by 40.0 gram bicarbonate of ammonia and 360 gram water, drip off and stirred 30 minutes, filter.Filter cake is with 25 ℃ water washing 3 times, after the 70-80 ℃ of oven dry manganous carbonate 17.4 grams; Filtrate is concentrated into dried ammonium sulfate 38.4 grams that obtain.
Embodiment 6
Get ammonium manganous sulfate crystal 80.0 grams, after 200 gram water dissolution, under 50 ℃, be added drop-wise in the solution that is made into by 40.0 gram bicarbonate of ammonia and 360 gram water, drip off and stirred 30 minutes, filter, filter cake is with 50 ℃ water washing 3 times, after the 70-80 ℃ of oven dry manganous carbonate 22.9 restrains; Filtrate is concentrated into dried ammonium sulfate 51.8 grams that obtain.
Claims (8)
1. one kind to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, it is characterized in that comprising the steps:
(1) Mn-bearing waste water of 1000 mass parts and the manganese waste slag that contains of 50 mass parts are put into reactor, stir the oxalic acid that adds 15～32 mass parts down, reacted 15～30 minutes down, filter then and obtain filtrate at 75～90 ℃; Describedly contain the Manganse Dioxide that manganese waste slag contains 20～40% quality, Mn-bearing waste water contains the sulfuric acid of 10% quality and the bivalent manganese of 50～60g/L;
(2) in the filtrate that step 1 obtains, add the superoxol of 5～10 mass parts, the massfraction that described peroxide is crossed hydrogen solution is 30%, the pH value that the ammonia soln that adds 110～125 mass parts simultaneously is neutralized to reaction system is 5.0～7.0, and the massfraction of described ammonia soln is 25%; Reacted 25～35 minutes down at 30～60 ℃, filter and obtain filtrate;
(3) filtrate that step 2 is obtained is heated to 55～65 ℃, add the ammonium sulfide solution of 3～5 mass parts, the massfraction of described ammonium sulfide solution is 5%, and the pH value that keeps reaction system simultaneously is 6.0～6.5, reacted 2 hours down at 60～65 ℃, filter and obtain filtrate;
(4) in the filtrate that step 3 obtains, add the ammonium sulfate of 30～60 mass parts, be heated to solid and dissolve fully, concentrate, crystallization, obtain the ammonium manganous sulfate crystal;
(5) with the ammonium manganous sulfate crystal with water dissolution after, join massfraction and be in 5～20% the ammonium bicarbonate soln, stirred 25～35 minutes down at 10～60 ℃, obtain filter cake and filtrate after the filtration respectively; Filtrate concentrating obtains ammonium sulfate, washes filter cake with water and dry to obtain manganous carbonate.
2. according to claim 1 to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, it is characterized in that: in the step 1, consumption of oxalic acid is 20～28 mass parts; Temperature is 80 ℃; Time is 20 minutes.
3. according to claim 1 to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, it is characterized in that: in the step 2, described hydrogen peroxide consumption is 5 mass parts; Ammonia volume is 110～120 mass parts; The pH value is 5.0～6.0; Temperature is 40 ℃.
4. according to claim 1 to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, it is characterized in that: in the step 3, described ammonium sulfide consumption is 4 mass parts; Temperature is 60 ℃.
5. according to claim 1 to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, it is characterized in that: in the step 4, described ammonium sulfate consumption is 30～40 mass parts.
6. according to claim 1 to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, it is characterized in that: in the step 5, the mass ratio of ammonium manganous sulfate and water is 1: 2～10; The mol ratio of ammonium manganous sulfate and bicarbonate of ammonia is 1: 2～4.
7. according to claim 1 to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, it is characterized in that: in the step 5, the massfraction of ammonium bicarbonate soln is 10%.
8. according to claim 1 to contain the method that manganese waste slag and waste water are the feedstock production manganous carbonate, it is characterized in that: in the step 5, described filter cake, is dried down at 70～80 ℃ then and is obtained manganous carbonate more than 3 times with 20～50 ℃ of water washings.
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| CN101805024B (en) * | 2010-04-27 | 2012-03-07 | 江苏大学 | Preparation method of manganese carbonate nanorod |
| CN103466830A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Method for recycling electrolytic manganese metal anode waste liquor |
| CN104628003B (en) * | 2015-02-02 | 2017-03-15 | 嘉应学院 | A kind of method that utilization sodium permanganate production waste residue produces potassium fluosilicate |
| CN108183207A (en) * | 2017-12-23 | 2018-06-19 | 湖南佳纳能源科技有限公司 | A kind of method that compound manganese ore prepares anode material of lithium battery |
| CN109095503A (en) * | 2018-07-18 | 2018-12-28 | 重庆上甲电子股份有限公司 | A method of manganese carbonate is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN109292825A (en) * | 2018-11-14 | 2019-02-01 | 宜宾学院 | A kind of Process of Hydroquinone Production waste water comprehensive reutilization method |
| CN112479260A (en) * | 2020-12-15 | 2021-03-12 | 南通第六元素材料科技有限公司 | Method for resource utilization of waste salt in graphene oxide production process |
| CN113860376A (en) * | 2021-11-04 | 2021-12-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity manganese carbonate by using vanadium extraction wastewater |
| CN114715943A (en) * | 2022-03-28 | 2022-07-08 | 中南大学 | Process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride and preparation method |
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