CN104710032A - Resource process suitable for manganese-containing wastewater in electrolytic manganese production process - Google Patents
Resource process suitable for manganese-containing wastewater in electrolytic manganese production process Download PDFInfo
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- CN104710032A CN104710032A CN201310683916.7A CN201310683916A CN104710032A CN 104710032 A CN104710032 A CN 104710032A CN 201310683916 A CN201310683916 A CN 201310683916A CN 104710032 A CN104710032 A CN 104710032A
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- water
- manganese
- reverse osmosis
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
- C02F1/003—Processes for the treatment of water whereby the filtration technique is of importance using household-type filters for producing potable water, e.g. pitchers, bottles, faucet mounted devices
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
Abstract
The invention relates to a resource process suitable for manganese-containing wastewater in an electrolytic manganese production process. The resource process is specifically characterized in that a chemical precipitation method is adopted to recover the manganese resource and a membrane process is adopted to recover ammonia nitrogen and achieve the discharge standard, wherein the precipitation process comprises an agent adding system, a precipitation system and a residue recovering system, the added reagents comprise sodium carbonate and sulfuric acid, and the membrane treatment process comprises sand filtration, nano-filtration and a reverse osmosis system. According to the present invention, during the operation process, the manganese-containing wastewater is subjected to chemical precipitation so as to remove most of manganese and part of calcium, the manganese residue is pumped into a subsequent treatment system through a pump, the carbonate manganese residue is recovered after dewatering, the supernatant enters a membrane treatment system, the clear liquid is directly discharged after the reverse osmosis deep treatment, the reverse osmosis concentrated liquid returns to the precipitation system to carry out a circulation treatment, and the nano-filtration concentrated liquid is subjected to ammonia nitrogen enrichment so as to be used for supplementing the ammonia for the electrolytic manganese production system; and the process has the following advantages that: the manganese-containing wastewater with various concentrations can be treated, the recovery of the manganese and the ammonia nitrogen can be achieved, various indicators of the effluent can meet the national first-order discharge standard, and the process is suitable for the wastewater treatment in the electrolytic manganese production industry.
Description
Technical field
The invention belongs to waste water reclaiming technical field, particularly a kind of technique being applicable to Mn-bearing waste water resource utilization in electrolytic manganese production process.
Background technology
Although China's electrolytic manganese industry starting is late, development is fast, has become electrolytic manganese production maximum in the world, outlet and consumption big country at present.Often produce 1t electrolytic manganese and will produce processing wastewater 10 ~ 25m
3, the factory effluent complicated component produced in electrolytic manganese production, pollution load weight, containing multiple pollutants such as total manganese, ammonia nitrogen, suspended substances in waste water, be rich in a large amount of calcium, magnesium ion, these materials are a kind of pollutent simultaneously, are also a kind of resources.
In the treatment process of process Mn-bearing waste water, conventional method has chemical precipitation and micro-electrolysis method.These class methods have higher removal efficiency to high concentration manganese ion, but will reach and meet emission standard requirement, still there is larger problem.Higher ph is needed just to make water outlet mn ion reach about 2mg/L as adopted calcium hydroxide precipitation method, go out water unstable, simultaneously because the introducing precipitation slag of a large amount of calcium ion is difficult to recycling, precipitation process is carried out as adopted sodium carbonate, water outlet mn ion is made to reach below 2mg/L, need pH value to control about 9.5, now, a large amount of calcium, magnesium precipitate thing are mixed into content and the recovery that directly can have influence on manganese in manganese slag in slag.And micro electrolysis tech is because its running cost is high, control difficulty is large, technology is more immature, also there is no engineer applied at present.Due to the complicacy of waste water, directly adopt all difficult success of the Novel reclamation such as membrane technique, ion exchange resin technology.This kind of technology can only process for metal ions such as Manganese in Waste Waters simultaneously, still lacks control for ammonia nitrogen in waste water.
At present, all there is different problem in the multiple process Mn-bearing waste water technology proposed, causes practical application project few.Publication number is the secondary flocculation sediment technique proposing NaOH+ carbonate+hydrogen peroxide in the patent of invention of CN102115284A, for qualified discharge needs to carry out multistage complex process and operation pH value > 9.5, in precipitation slag, Fe content is low, and cannot process ammonia nitrogen.Publication number is propose dual-membrane process in the patent of invention of CN103172194A and CN102728230A, the subject matter that this technique exists is that operational process film load is high, operational conditions is harsh, operation easier is high, be difficult to ensure steady in a long-term operation, there is wild effect in water outlet ammonia nitrogen, need to set up Filtration Adsorption system, increase running cost.Publication number is the method that the patent of invention of CN102464372A proposes to extract, but is only applicable to the process of lower concentration Mn-bearing waste water.Publication number is that the patent of invention of CN101838064A and CN102120658A proposes the method adopting resins exchange mode to reclaim Manganese in Waste Water and ammonia nitrogen respectively, but be difficult in actual applications realize the separately process of manganese, ammonia nitrogen by resin, for the combined pollution waste water of the actual generation of electrolytic manganese factory, cannot realize reclaiming manganese and ammonia nitrogen respectively.
Summary of the invention
The present invention proposes a kind of technique being applicable to Mn-bearing waste water resource utilization in electrolytic manganese production process, can be realized the resource utilization recovery of manganese, ammonia nitrogen by chemical precipitation and membrane concentration, after making process, water outlet meets GB8978-96 " integrated wastewater discharge standard " first discharge standard simultaneously.
The technical scheme that the present invention proposes is, be applicable to a technique for Mn-bearing waste water resource utilization in electrolytic manganese production process, it is characterized in that: after Mn-bearing waste water reclaims manganese slag by chemical precipitation, clear liquid enters membranous system, reclaim ammonia nitrogen by concentrated solution, clear liquid realizes qualified discharge.
Its specific embodiment comprises the steps:
(1) chemistry precipitation reagents is sodium carbonate, proof dry powder feeding or solution is selected to add form, different according to different dissolves carbonate degree, dosage number directly can control the content of manganous carbonate in throw out, adding amount of reagent directly can feed back according to pH value after reaction.Reagent joins in waste water, fully stirs after mixing, the residence time >=60min, enter in post precipitation pond, design the residence time >=24 hours.
Principal reaction is:
Mn
2++CO
3 2-＝MnCO
3↓ksp＝1.8×10
-11
Side reaction:
Ca
2++CO
3 2-＝CaCO
3↓ksp＝2.8×10
-9
Mg
2++CO
3 2-＝MgCO
3↓ksp＝3.5×10
-8
In formula, Ksp represents solubility product constant.
(2) supernatants after precipitation and sulphuric acid soln are mixed into equalizing tank, fully after mixing, flow into clean water basin, for ensureing the stability of subsequent film system, ensure that clean water basin water body pH scope is 6.5 ~ 7.0.
(3) through pump, waste water is squeezed into sand filtration after and filter removal suspended particle, enter nanofiltration system, by regulating, make clear water producing water ratio > 90%, ensure concentrated about 10 times of ammonia nitrogen in dense water, by this NF concentrated water reuse to electrolytic manganese production system preparation ammoniacal liquor, clear water produces water and enters reverse osmosis system; Reverse osmosis system carries out advanced treatment to clear water, clear water producing water ratio > 85%, and producing water can directly discharge, and also can be used for preparing sodium carbonate solution, dense water is got back in clean water basin and circulated.
Be applicable to a technique for Mn-bearing waste water resource utilization in electrolytic manganese production process as above, its chemical precipitation system features is:
A. sodium carbonate selected by dosing reagent, settling tank supernatant liquor pH scope 8.5 ~ 8.7;
B. Fe content > 35% (dry weight disregards moisture content) in manganese slag is precipitated.
Be applicable to a technique for Mn-bearing waste water resource utilization in electrolytic manganese production process as above, its film processing system is characterised in that:
A. clean water basin pH scope 6.5 ~ 7.0 before film is entered;
B. nanofiltration NF concentrated water reuse electrolytic manganese production system preparation ammonia solution;
C. nanofiltration clear water producing water ratio >=90%, working pressure 1.2 ~ 2.0MPa;
D. reverse osmosis concentrated water gets back to clean water basin;
E. reverse osmosis clear water producing water ratio >=85%, working pressure 1 ~ 2.0MPa.
Advantage: the present invention is by the combination of chemical precipitation and membrane concentration technology, and can realize manganese, the resource utilization of ammonia nitrogen reclaims, after making process, water outlet meets GB8978-96 " integrated wastewater discharge standard " first discharge standard simultaneously.Method of chemical treatment water outlet manganese can not only be overcome, ammonia nitrogen is unstable, cannot the shortcoming of qualified discharge, play it efficient, simple advantage, but also can by constant for film process effluent quality, processing efficiency is high, the combination of advantages that can concentrate resource utilization is come in, by the Advantages found of two kinds of techniques out, the shortcoming of two kinds of techniques is overcome simultaneously, various concentration Mn-bearing waste water can be processed, the recovery of manganese and ammonia nitrogen can be realized, water outlet indices can meet national grade one discharge standard, be particularly useful for the recycling treatment that electrolytic manganese enterprise produces waste water, but be not limited only to this.
Accompanying drawing explanation
A kind of process flow sheet being applicable to Mn-bearing waste water resource utilization in electrolytic manganese production process of Fig. 1 the present invention
Embodiment
Composition graphs 1, a kind of technique being applicable to Mn-bearing waste water resource utilization in electrolytic manganese production process of the present invention, its specific embodiment is as follows:
(1) after Mn-bearing waste water collects water collecting basin, enter agitated pool, add carbonate reagent simultaneously, sodium carbonate feed postition can adopt direct proof dry powder feeding or obtain solution to add two kinds of modes.According to agitated pool pH value and settling tank supernatant liquor pH value, regulate sodium carbonate add-on, agitated pool pH span of control 9.4 ~ 9.6, settling tank supernatant liquor pH value range 8.5 ~ 8.7.Ensure Fe content > 35% (dry weight) in precipitation slag.
(2) agitated pool churning time > 1 hour, settling tank residence time > 24 hours, supernatant liquor entered the mixing of equalizing tank sulfuric acid, and when ensureing that water outlet enters clean water basin, pH is 6.5 ~ 7.0.
(3) supernatant liquor is driven into membranous system through pump, first filters suspended particle by sand filtration, then enters nanofiltration system, controls nanofiltration clear water producing water ratio, usual nanofiltration clear water producing water ratio >=90%, working pressure 1.2 ~ 2.0MPa according to effluent quality; Nanofiltration clear water enters reverse osmosis system, and NF concentrated water reuse is in electrolytic manganese production system preparation ammoniacal liquor.According to the water yield and water quality, can select to adopt one-level nanofiltration or multistage nanofiltration form, every grade of nanofiltration can select the form of branched nanofiltration membrane parallel connection.
(4) after nanofiltration system clear water enters reverse osmosis, reverse osmosis clear water is except on a small quantity for rinsing nanofiltration membrane, and all the other all can directly discharge, and also can be used for sodium carbonate solution preparation, dense water is back to clean water basin or nanofiltration.Reverse osmosis clear water producing water ratio >=85%, working pressure 1.0 ~ 2.0MPa, can regulate according to draining water quality.According to the water yield and water quality, can select to adopt first-stage reverse osmosis or multi-stage reverse osmosis form, every grade of reverse osmosis can select the form of branched reverse osmosis membrane parallel connection.
Its specific embodiment has:
Embodiment 1: select sodium carbonate proof dry powder feeding form, settling tank supernatant liquor pH=9.5, nanofiltration clear water producing water ratio=92%, working pressure 1.6MPa, reverse osmosis clear water producing water ratio=85%, working pressure 1.5MPa;
Water collecting basin waste water quality: 20m
3/ h, pH=6.4, Mn
2+concentration 1841mg/L, NH
4 +concentration 980mg/L.Agitated pool residence time 60min, settling tank residence time 24h.Under these conditions, Fe content 39.4% (doing) in manganese slag, nanofiltration reusing concentrated water ammonia nitrogen 5040mg/L, reverse osmosis draining NH
4 +concentration 6mg/L, Mn
2+concentration 0.2mg/L.
Embodiment 2: select sodium carbonate proof dry powder feeding form, settling tank supernatant liquor pH=9.6, nanofiltration clear water producing water ratio=93%, working pressure 1.7MPa, reverse osmosis clear water producing water ratio=86%, working pressure 1.5MPa;
Water collecting basin waste water quality: 20m
3/ h, pH=6.5, Mn
2+concentration 1788mg/L, NH
4 +concentration 1020mg/L.Agitated pool residence time 60min, settling tank residence time 24h.Under these conditions, Fe content 38.7% (doing) in manganese slag, nanofiltration reusing concentrated water ammonia nitrogen 5543mg/L, reverse osmosis draining NH
4 +concentration 8mg/L, Mn
2+concentration 0.2mg/L.
Embodiment 3: select sodium carbonate proof dry powder feeding form, settling tank supernatant liquor pH=9.7, nanofiltration clear water producing water ratio=93%, working pressure 1.7MPa, reverse osmosis clear water producing water ratio=86%, working pressure 1.6MPa;
Water collecting basin waste water quality: 20m
3/ h, pH=6.7, Mn
2+concentration 1755mg/L, NH
4 +concentration 957mg/L.Agitated pool residence time 60min, settling tank residence time 24h.Under these conditions, Fe content 37.6% (doing) in manganese slag, nanofiltration reusing concentrated water ammonia nitrogen 5132mg/L, reverse osmosis draining NH
4 +concentration 7mg/L, Mn
2+concentration 0.3mg/L.
Embodiment 4: select sodium carbonate solution (20%) to add form, settling tank supernatant liquor pH=9.5, nanofiltration clear water producing water ratio=92%, working pressure 1.6MPa, reverse osmosis clear water producing water ratio=85%, working pressure 1.5MPa;
Water collecting basin waste water quality: 20m
3/ h, pH=6.7, Mn
2+concentration 1676mg/L, NH
4 +concentration 850mg/L.Agitated pool residence time 60min, settling tank residence time 24h.Under these conditions, Fe content 39.8% (doing) in manganese slag, nanofiltration reusing concentrated water ammonia nitrogen 4998mg/L, reverse osmosis draining NH4+ concentration 3mg/L, Mn
2+concentration 0.2mg/L.
Embodiment 5: select sodium carbonate solution (20%) to add form, settling tank supernatant liquor pH=9.6, nanofiltration clear water producing water ratio=93%, working pressure 1.7MPa, reverse osmosis clear water producing water ratio=87%, working pressure 1.6MPa;
Water collecting basin waste water quality: 20m
3/ h, pH=6.6, Mn
2+concentration 1901mg/L, NH
4 +concentration 873mg/L.Agitated pool residence time 60min, settling tank residence time 24h.Under these conditions, Fe content 38.5% (doing) in manganese slag, nanofiltration reusing concentrated water ammonia nitrogen 5111mg/L, reverse osmosis draining NH
4 +concentration 7mg/L, Mn
2+concentration 0.3mg/L.
Embodiment 6: select sodium carbonate solution (20%) to add form, settling tank supernatant liquor pH=9.7, nanofiltration clear water producing water ratio=93%, working pressure 1.7MPa, reverse osmosis clear water producing water ratio=86%, working pressure 1.6MPa;
Water collecting basin waste water quality: 20m
3/ h, pH=6.7, Mn
2+concentration 1876mg/L, NH
4 +concentration 1024mg/L.Agitated pool residence time 60min, settling tank residence time 24h.Under these conditions, Fe content 36.8% (doing) in manganese slag, nanofiltration reusing concentrated water ammonia nitrogen 5251mg/L, reverse osmosis draining NH
4 +concentration 6mg/L, Mn
2+concentration 0.3mg/L.
Claims (3)
1. be applicable to a technique for Mn-bearing waste water resource utilization in electrolytic manganese production process, it is characterized in that: after Mn-bearing waste water reclaims manganese slag by chemical precipitation, clear liquid enters membranous system, reclaims ammonia nitrogen by concentrated solution, and clear liquid realizes qualified discharge, its concrete technology step:
(1) chemistry precipitation reagents is sodium carbonate, proof dry powder feeding or solution is selected to add form, different according to different dissolves carbonate degree, dosage number directly can control the content of manganous carbonate in throw out, adding amount of reagent directly can feed back according to pH value after reaction.Reagent joins in waste water, fully stirs after mixing, the residence time >=60min, enter in post precipitation pond, design the residence time >=24 hours;
(2) supernatants after precipitation and sulphuric acid soln are mixed into equalizing tank, fully after mixing, flow into clean water basin, for ensureing the stability of subsequent film system, ensure that clean water basin water body pH scope is 6.5 ~ 7.0;
(3) through pump, waste water is squeezed into sand filtration after and filter removal suspended particle, enter nanofiltration system, by regulating, make clear water producing water ratio > 90%, ensure concentrated about 10 times of ammonia nitrogen in dense water, by this NF concentrated water reuse to electrolytic manganese production system preparation ammoniacal liquor, clear water produces water and enters reverse osmosis system; Reverse osmosis system carries out advanced treatment to clear water, clear water producing water ratio > 85%, and producing water can directly discharge, and also can be used for preparing sodium carbonate solution, dense water is got back in clean water basin and circulated.
2. a kind of technique being applicable to Mn-bearing waste water resource utilization in electrolytic manganese production process as claimed in claim 1, its chemical precipitation system features is:
A. sodium carbonate selected by dosing reagent, settling tank supernatant liquor pH scope 8.5 ~ 8.7;
B. Fe content > 35% (dry weight disregards moisture content) in manganese slag is precipitated.
3. a kind of technique being applicable to Mn-bearing waste water resource utilization in electrolytic manganese production process as claimed in claim 1, its film processing system is characterised in that:
A. clean water basin pH scope 6.5 ~ 7.0 before film is entered;
B. nanofiltration NF concentrated water reuse electrolytic manganese production system preparation ammonia solution;
C. nanofiltration clear water producing water ratio >=90%, working pressure 1.2 ~ 2.0MPa;
D. reverse osmosis concentrated water gets back to clean water basin;
E. reverse osmosis clear water producing water ratio >=85%, working pressure 1 ~ 2.0MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761327A (en) * | 2019-03-13 | 2019-05-17 | 联化科技(盐城)有限公司 | Processing method without aluminum ions waste water |
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2013
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Application publication date: 20150617 |