CN105967396A - Method for treating manganese-containing wastewater - Google Patents
Method for treating manganese-containing wastewater Download PDFInfo
- Publication number
- CN105967396A CN105967396A CN201610489434.1A CN201610489434A CN105967396A CN 105967396 A CN105967396 A CN 105967396A CN 201610489434 A CN201610489434 A CN 201610489434A CN 105967396 A CN105967396 A CN 105967396A
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- CN
- China
- Prior art keywords
- manganese
- waste water
- bearing waste
- processing method
- gas
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses a method for treating manganese-containing wastewater. The method includes steps of (1), adding alkaline substances into the manganese-containing wastewater; (2), filling the manganese-containing wastewater with gas with CO2 in stirring states and carrying out reaction; (3), separating solid from solution after the reaction is completed to obtain the manganese carbonate solid and the solution without manganese. The method for treating the manganese-containing wastewater has the advantages that the manganese-containing wastewater is treated by waste, and is filled with the waste gas which is leached by the aid of sulfuric acid in electrolytic manganese production procedures or generated in boilers by means of combustion in the electrolytic manganese production procedures and contains the carbon dioxide, the few alkaline substances are added into the manganese-containing wastewater, accordingly, manganese resources in the manganese-containing wastewater can be effectively recycled, and the method has certain economic value; the generated solution without the manganese can be recycled during electrolytic manganese, electrolytic manganese dioxide or electrolytic manganeous-manganic oxide production, waste generation can be prevented in integral procedures, and accordingly environments can be protected.
Description
Technical field
The present invention relates to field of waste water treatment, particularly relate in hydrometallurgy (such as electrolytic manganese, electrolytic manganese dioxide) production process
The process technique of the Mn-bearing waste water produced.
Background technology
In recent years, China's electrolytic manganese Industry Quick Development, production capacity is drastically expanded, and makes China become the electrolytic manganese life of maximum in the world
Produce, export and country of consumption.Current electrolysis manganese mainly uses the method for sulfuric acid leaching manganese carbonate ore to produce, and produces big in leaching process
The carbon dioxide containing gas of amount, is directly discharged in air.During electrolytic manganese production, can produce substantial amounts of wash plate waste water,
Rinse groove face waste water, ground flushing water, sheet frame cleans waste water, the Mn-bearing waste water such as filter cloth waste water, slag storehouse penetrating fluid is rinsed in filter pressing,
It typically 1～about 3g/L containing manganese concentration, also has and is up to more than 20g/L containing manganese.Due in these Mn-bearing waste waters in addition to containing manganese,
Possibly together with NH4+、Ca2+、Mg2+、Cd6+Deng, waste water quality is complicated, and pH is relatively low, and intractability is bigger.Directly discharge
Natural environment can be caused severe contamination, and cause the waste of promoter manganese.It is therefore desirable to Mn-bearing waste water is carried out effectively
Purify so that it is recycle, while reducing environmental pollution, improve the utilization ratio of resource.
At present Treatment of Wastewater With Manganese method is mainly had the sides such as alkalization manganese removal, carbonate manganese removal, ion exchange, film process
Method.Wherein alkalization manganese removal is usually Calx, NaOH, NaHCO3It is added in Mn-bearing waste water Deng alkaline matter, treating
The pH value processing water brings up to more than 9.5, Mn2+MnO promptly it is oxidized under the effect of dissolved oxygen2Separate out, thus reach
The purpose of demanganization.The method is simple, but the alkaline matter such as superfluous lime added makes the solution alkaline after demanganization, no
Can directly discharge, and product contains after demanganization more unreacted Calx, need to consume too much acid, thus cause this
Method cannot be economical utilization.Carbonate manganese removal needs to carry out at temperature is more than 20 DEG C and it needs to pH is 8.8～9 in control,
Carbonate consumption is more than the 200% of theoretical amount, although the method can process certain density manganese containing solution, however it is necessary that and disappears
Consuming substantial amounts of reagent, operating cost is high.Ion exchange demanganization or film process Mn-bearing waste water to be needed to use substantial amounts of amberlite
Fat or ultrafilter membrane, reverse osmosis membrane etc., ion exchange resin, ultrafilter membrane, reverse osmosis membrane are relatively costly, so that these methods
Operating cost increase, apply limited.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that the side processing Mn-bearing waste water of a kind of low cost
Method.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is:
The processing method of a kind of Mn-bearing waste water, comprises the following steps:
(1) in Mn-bearing waste water, alkaline matter is added；
(2) CO will be contained when stirring2Gas be passed through in Mn-bearing waste water and react；
(3) carry out solid-liquid separation after having reacted, obtain manganese carbonate solid and demanganization solution.
The processing method of above-mentioned Mn-bearing waste water, it is preferred that described containing CO2Gas be to use sulphuric acid during electrolytic manganese production
Leach produce containing CO2Waste gas, during electrolytic manganese production boiler combustion produce containing CO2Waste gas.
The processing method of above-mentioned Mn-bearing waste water, it is preferred that described containing CO2Gas intake is theoretical amount 1.5～10
Times；Described theoretical amount refers to Mn in Mn-bearing waste water2+It is fully converted to the theoretical amount needed for manganese carbonate, is passed through the CO of excess2
Manganese in solution can be removed to relatively low content by gas.Demanganization condition has been done substantial amounts of research and experiment by applicant, finds
CO2Intake at least can be only achieved preferable demanganization effect for more than 1.5 times in excess, and its intake more than more than 10 times time,
Then little to demanganization effect of depth, therefore select the CO of 1.5～10 times2Theoretical intake.
The processing method of above-mentioned Mn-bearing waste water, it is preferred that one or more in ammonia, quick lime of described alkaline matter,
Nertralizer conventional during wherein ammonia is leaching process, and quick lime is due to cheap and easy to get, can use as auxiliary additive, fall
Low operating cost.
The processing method of above-mentioned Mn-bearing waste water, it is preferred that in described step (1), adds alkaline matter extremely in Mn-bearing waste water
The pH value of Mn-bearing waste water is 6～8.Inventor finds still have when pH relatively low (such as pH=6) by substantial amounts of research and experiment
Preferably demanganization effect, is therefore disposably to regulate the pH value of solution when reaction starts to put in place, solution in course of reaction
PH value can be gradually lowered, and at the end of reaction, solution ph maintains 6～about 7, it is easy to direct reuse, it is to avoid the weight of pH
Polyphony saves.
The processing method of above-mentioned Mn-bearing waste water, it is preferred that described Mn-bearing waste water refers to electrolytic manganese, electrolytic manganese dioxide, electrolysis
The middle low concentration Mn-bearing waste water produced during mangano-manganic oxide；The Mn of described middle low concentration Mn-bearing waste water2+Concentration range is
200mg/L～25g/L.
The processing method of above-mentioned Mn-bearing waste water, it is preferred that described demanganization solution returns electrolytic manganese, electrolytic manganese dioxide or electrolysis
The production of mangano-manganic oxide re-uses；Described manganese carbonate solid enters sulfuric acid leaching groove, uses as nertralizer, alternative
Partial ammonia water, on the one hand reduces the usage amount of ammonia, reduces cost, is on the other hand reused by the manganese in Mn-bearing waste water, carries
The utilization rate of manganese in high production process.
The processing method of above-mentioned Mn-bearing waste water, it is preferred that the mode of described solid-liquid separation be natural subsidence separate, use dense
Machine separation, filter pressing separation or vacuum filtration separate.
The present invention utilizes the waste gas containing manganese dioxide produced in production process as carbon source, is blown in Mn-bearing waste water, passes through ammonia
Deng the pH value of alkaline matter regulation manganese containing solution, thus being precipitated out by the manganese in waste water, its principle is as follows:
MnSO4+2(OH-)+CO2→MnCO3+SO4 2-+H2O。
Compared with prior art, it is an advantage of the current invention that:
(1) processing method of the Mn-bearing waste water of the present invention is the treatment of wastes with processes of wastes against one another, use use during electrolytic manganese production sulfuric acid leaching or
The carbonated waste gas that during electrolytic manganese production, boiler combustion produces, and add a small amount of alkaline matter, it is possible to manganese will be contained
Manganese in Waste Water resource effectively reclaims, and has certain economic worth；The demanganization solution simultaneously produced can return electrolytic manganese,
Re-using in the production of electrolytic manganese dioxide or electrolysis mangano-manganic oxide, whole process no waste produces, and protects environment.
(2) consumption of raw materials that the processing method of the Mn-bearing waste water of the present invention is used is few, low cost, and the nertralizer used is
Producing conventional nertralizer ammonia and quick lime cheap and easy to get, concrete application is the most limited by cost.
(3) during the processing method of the Mn-bearing waste water of the present invention, demanganization efficiency is high, due to the CO used2Can be significantly excessive,
Promote the carrying out of demanganization reaction, the manganese concentration in Mn-bearing waste water can be down to below 50mg/L.
Marginal data
Fig. 1 is the process chart of the processing method of the Mn-bearing waste water of the embodiment of the present invention 1.
Detailed description of the invention
For the ease of understanding the present invention, hereafter the present invention is made more comprehensively, describes meticulously by preferred embodiment, but the present invention
Protection domain be not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art is identical.
Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the protection model of the present invention
Enclose.
Except there being special instruction, the various reagent used in the present invention, raw material are can commodity commercially or permissible
The product prepared by known method.
Embodiment 1:
A kind of processing method of the Mn-bearing waste water of the present invention, process chart is as it is shown in figure 1, comprise the following steps:
(1) Mn in this pending Mn-bearing waste water (Xi Banshui produced during electrolytic manganese) is measured2+Concentration is 200mg/L；
(2) take the pending Mn-bearing waste water of 200L and put in reactor, be subsequently adding the ammonia that 360mL concentration is 17%, regulation
PH value to Mn-bearing waste water is 6.5；
(3) under conditions of stirring, Mn-bearing waste water after step (2) processes is passed through during electrolytic manganese production and uses sulphuric acid
Leach produce containing CO2Waste gas (CO in this waste gas2Concentration is 10%), the flow velocity being passed through waste gas is 20L/min, is passed through
The time of gas is 85min 10 times of theoretical amount (intake of carbon dioxide be), after question response terminates, is used by solution dense
Close machine carries out solid-liquid separation, obtains manganese carbonate solid and demanganization solution；The manganese carbonate solid of gained enter sulfuric acid leaching groove as in
Mediating recipe uses, and the demanganization solution (manganese concentration is reduced to 18mg/L) of gained returns in electrolytic manganese production and re-uses.
Embodiment 2:
The processing method of the Mn-bearing waste water of a kind of present invention, comprises the following steps:
(1) Mn in this pending Mn-bearing waste water (Xi Banshui produced during electrolytic manganese) is measured2+Concentration is 4200mg/L；
(2) taking the pending Mn-bearing waste water of 200L to add in reactor, be subsequently adding 1709g quick lime, regulation is to Mn-bearing waste water
PH value be 7.5；
(3) stirring under conditions of to step (2) process after Mn-bearing waste water in be passed through boiler combustion produce containing CO2Useless
Gas (CO in this waste gas2Concentration is 8%), the flow velocity being passed through waste gas is 100L/min, and the time being passed through gas is 214min (two
The intake of carbonoxide is 5 times of theoretical amount), after question response terminates, solution use vacuum filtration machine carry out solid-liquid separation,
To manganese carbonate solid and demanganization solution；The manganese carbonate solid of gained enters sulfuric acid leaching groove and uses as nertralizer, the demanganization of gained
Solution (manganese concentration is reduced to 35mg/L) returns in electrolytic manganese production and re-uses.
Embodiment 3:
The processing method of the Mn-bearing waste water of a kind of present invention, comprises the following steps:
(1) Mn in this pending Mn-bearing waste water (slag field penetrating fluid during electrolytic manganese) is measured2+Concentration is 25000mg/L；
(2) taking the pending Mn-bearing waste water of 200L and add in reactor, adding 10L concentration is the ammonia of 17%, then is dividedly in some parts
7462g quick lime, the pH value of regulation to Mn-bearing waste water is 7.8；
(3) stirring under conditions of to step (2) process after Mn-bearing waste water in be passed through boiler combustion produce containing CO2Useless
Gas 1.5 times of theoretical amount (intake of carbon dioxide be), after question response terminates, uses concentrator to carry out solid-liquid separation by solution,
Obtain manganese carbonate solid and demanganization solution；The manganese carbonate solid of gained enters sulfuric acid leaching groove and uses as nertralizer, removing of gained
Manganese solution (manganese concentration is reduced to 48mg/L) returns in electrolytic manganese production and re-uses.
Claims (8)
1. the processing method of a Mn-bearing waste water, it is characterised in that comprise the following steps:
(1) in Mn-bearing waste water, alkaline matter is added；
(2) CO will be contained when stirring2Gas be passed through in Mn-bearing waste water and react；
(3) carry out solid-liquid separation after having reacted, obtain manganese carbonate solid and demanganization solution.
2. the processing method of Mn-bearing waste water as claimed in claim 1, it is characterised in that described containing CO2Gas be electrolytic manganese
In production process use sulfuric acid leaching produce containing CO2Waste gas, during electrolytic manganese production boiler combustion produce containing CO2's
Waste gas.
3. the processing method of Mn-bearing waste water as claimed in claim 1, it is characterised in that described containing CO2The intake of gas
For theoretical amount 1.5～10 times.
4. the processing method of Mn-bearing waste water as claimed in claim 1, it is characterised in that described alkaline matter is selected from ammonia, life
One or more in Calx.
5. the processing method of Mn-bearing waste water as claimed in claim 1, it is characterised in that in described step (1), to containing manganese
In waste water, addition alkaline matter is 6～8 to the pH value of Mn-bearing waste water.
6. the processing method of the Mn-bearing waste water as described in any one of Claims 1 to 5, it is characterised in that described Mn-bearing waste water is
Refer to the middle low concentration Mn-bearing waste water produced in electrolytic manganese, electrolytic manganese dioxide, electrolysis mangano-manganic oxide production process；In described low
The Mn of concentration Mn-bearing waste water2+Concentration range is 200mg/L～25g/L.
7. the processing method of the Mn-bearing waste water as described in any one of Claims 1 to 5, it is characterised in that described demanganization solution returns
Return in the production of electrolytic manganese, electrolytic manganese dioxide or electrolysis mangano-manganic oxide and re-use；Described manganese carbonate solid enters sulphuric acid leaching
Go out groove, use as nertralizer.
8. the processing method of the Mn-bearing waste water as described in any one of Claims 1 to 5, it is characterised in that described solid-liquid separation
Mode is that natural subsidence separates, uses concentrator separation, filter pressing separation or vacuum filtration to separate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610489434.1A CN105967396A (en) | 2016-06-29 | 2016-06-29 | Method for treating manganese-containing wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610489434.1A CN105967396A (en) | 2016-06-29 | 2016-06-29 | Method for treating manganese-containing wastewater |
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| CN201610489434.1A Pending CN105967396A (en) | 2016-06-29 | 2016-06-29 | Method for treating manganese-containing wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109019694A (en) * | 2018-10-25 | 2018-12-18 | 中国科学院青海盐湖研究所 | Micro-nano structure ball-type MnCO3Preparation method |
| CN109354270A (en) * | 2018-11-07 | 2019-02-19 | 长安大学 | A kind of method that Mancozeb production waste water is used without discharge cycle |
| CN109499042A (en) * | 2018-12-06 | 2019-03-22 | 城口县生产力促进中心 | A kind of method of soluble manganese ions stabilization processes in electrolytic manganese residues |
| CN113277654A (en) * | 2021-05-28 | 2021-08-20 | 金川集团股份有限公司 | Method and device for treating electrodeposition high-purity manganese waste liquid by using electrochemical method |
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| CN1587423A (en) * | 2004-07-21 | 2005-03-02 | 清华大学 | Method for recovering manganese from low content manganese carbonate raw ore |
| CN1919755A (en) * | 2006-09-15 | 2007-02-28 | 合肥工业大学 | Method of processing organic contaminant waste-water difficult to biochemical degradation using tetravalent manganese compounds |
| CN102260797A (en) * | 2011-07-22 | 2011-11-30 | 湘潭电化集团有限公司 | Production process for reclaiming manganese from manganese-containing waste water and waste slag by using waste gas |
| WO2012106181A2 (en) * | 2011-01-31 | 2012-08-09 | Chevron U.S.A. Inc. | Method for treating effluent waters |
| CN105039718A (en) * | 2015-09-11 | 2015-11-11 | 长沙矿冶研究院有限责任公司 | Comprehensive recycling method of electrolytic manganese anolyte |
-
2016
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5778988A (en) * | 1980-11-05 | 1982-05-17 | Kurita Water Ind Ltd | Treatment of waste water of waste gas desulfurization |
| CN1587423A (en) * | 2004-07-21 | 2005-03-02 | 清华大学 | Method for recovering manganese from low content manganese carbonate raw ore |
| CN1919755A (en) * | 2006-09-15 | 2007-02-28 | 合肥工业大学 | Method of processing organic contaminant waste-water difficult to biochemical degradation using tetravalent manganese compounds |
| WO2012106181A2 (en) * | 2011-01-31 | 2012-08-09 | Chevron U.S.A. Inc. | Method for treating effluent waters |
| CN102260797A (en) * | 2011-07-22 | 2011-11-30 | 湘潭电化集团有限公司 | Production process for reclaiming manganese from manganese-containing waste water and waste slag by using waste gas |
| CN105039718A (en) * | 2015-09-11 | 2015-11-11 | 长沙矿冶研究院有限责任公司 | Comprehensive recycling method of electrolytic manganese anolyte |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109019694A (en) * | 2018-10-25 | 2018-12-18 | 中国科学院青海盐湖研究所 | Micro-nano structure ball-type MnCO3Preparation method |
| CN109354270A (en) * | 2018-11-07 | 2019-02-19 | 长安大学 | A kind of method that Mancozeb production waste water is used without discharge cycle |
| CN109354270B (en) * | 2018-11-07 | 2021-11-16 | 长安大学 | Method for recycling mancozeb production wastewater without discharge |
| CN109499042A (en) * | 2018-12-06 | 2019-03-22 | 城口县生产力促进中心 | A kind of method of soluble manganese ions stabilization processes in electrolytic manganese residues |
| CN113277654A (en) * | 2021-05-28 | 2021-08-20 | 金川集团股份有限公司 | Method and device for treating electrodeposition high-purity manganese waste liquid by using electrochemical method |
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Application publication date: 20160928 |