CN102276070A - Composite reagent for separating calcium ions and magnesium ions from manganiferous waste water - Google Patents
Composite reagent for separating calcium ions and magnesium ions from manganiferous waste water Download PDFInfo
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- CN102276070A CN102276070A CN2011101431152A CN201110143115A CN102276070A CN 102276070 A CN102276070 A CN 102276070A CN 2011101431152 A CN2011101431152 A CN 2011101431152A CN 201110143115 A CN201110143115 A CN 201110143115A CN 102276070 A CN102276070 A CN 102276070A
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Abstract
The invention discloses a composite reagent for separating calcium ions and magnesium ions from manganiferous wastewater. The composite reagent is characterized by specifically comprising the following components: 34-39% of Na<+>, 2-4% of Cu<2+>, 1-3% of Fe<2+>, 8-10% of NH<4+>, 0.5-1.5% of Al<3+>, 21-24% of HCO3<->, 19-22% of F<->, 5-8% of Cl<->and 0.5-1% of SO4<2->. The use method of the composite reagent comprises the step of directly adding the composite reagent in a dry powder form to be mixed with raw manganiferous wastewater, or preparing the composite reagent into a solution and adding the composite reagent solution into the raw manganiferous wastewater, wherein the composite reagent in the prepared solution accounts for 25-40% in terms of mass fraction. After the composite reagent is mixed with the manganiferous wastewater, calcium ions and magnesium ions in the wastewater are subjected to chemical reaction and generate precipitates through complexing and flocculation actions, and the precipitates are removed through filtering. The composite reagent has the advantages of simplicity in preparation, wide raw material sources, suitability for a wide pH value range, high removal rate on calcium/magnesium ions and low magnesium ion loss rate being lower than 0.2%, and is suitable for the treatment of manganiferous wastewater with various ionic concentrations.
Description
Technical field
The invention belongs to technical field of waste water processing, particularly a kind of complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion.
Background technology
In the manganese ore district, slagheap factory has a large amount of waste water and produces, and its wastewater discharge is big, water quality is complicated, contains a large amount of metal ions, as direct discharging, with serious environment pollution, causes the loss of manganese resource simultaneously again.With being used for electrolytic manganese production after this waste water reclamation processing, can realize the utilization of manganese resources effective.But this type of waste water contains a large amount of calcium, magnesium ion, can influence the efficient and the life-span of used nanofiltration membrane in the subsequent technique in treating processes, also can impact electrolytic manganese production technology simultaneously.
According to part calcium, the long-pending constant of reactive magnesium resultant concentration is little, and much smaller than the long-pending constant of corresponding manganic compound concentration, available reagent is to calcium, magnesium ion precipitates removal, reagent commonly used has fluorochemical, phosphoric acid salt and carbonate reagent, but the Calcium Fluoride (Fluorspan) that uses the fluorochemical precipitation agent to be generated separately, magnesium fluoride throw out crystal grain is minimum, has only 5nm, bring great difficulty for follow-up filtration, because throw out filters not exclusively, can cause calcium in the raw wastewater solution, magnesium precipitate still exists, and causes calcium, the magnesium ion clearance is not high, simultaneously because the existence of precipitation crystal grain, can there be the effect of stopping up and polluting for follow-up nanofiltration membrane, has a strong impact on the life-span of nanofiltration membrane.Owing to manganese ion concentration in the original solution is higher, can there be MnF in addition in the part
2Precipitation causes the loss of mn ion, and wants to reach calcium, magnesium ion removal effect completely, and the required reaction times is extremely long, makes troubles for the enforcement of actual engineering, increases cost of investment.Phosphoric acid salt and carbonate precipitation method can cause a large amount of losses of mn ion, are not suitable for the recycling of Mn-bearing waste water.Therefore, by selecting a kind of suitable complex reagent for use, can realize the high efficiency separation of calcium in the Mn-bearing waste water, magnesium ion on the one hand, and the mn ion rate of loss can guarantee follow-up filtering efficient and recycling efficient on the other hand less than 0.2%.
Wherein, the long-pending constant of concentration is represented the product of the electrolytical saturated solution intermediate ion of indissoluble concentration power.
Summary of the invention
The present invention proposes a kind of complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion, by adding reagent preparation, can realize high calcium, magnesium ion clearance, and the mn ion rate of loss is less than 0.2% purpose simultaneously.
A kind of complex reagent that separates calcium in the Mn-bearing waste water, magnesium ion of the present invention, its concrete component feature be,
Component Na
+Content 34～39%, component C u
2+Content 2～4%,
Component Fe
2+Content 1～3%, component NH
4 +Content 8～10%,
Component Al
3+Content 0.5～1.5%, component HCO
3 -Content 21～24%,
Component F
-Content 19～22%, component C l
-Content 5～8%,
Component SO
4 2-Content 0.5～1%
A kind of using method of separating the complex reagent of calcium in the Mn-bearing waste water, magnesium ion of the present invention is, adopt chemical precipitation method, the complex reagent that in Mn-bearing waste water, adds preparation, can effectively promote the formation of calcium, magnesium precipitate on the one hand, and impel crystal grain to grow up fast by flocculation, the complexing action of other metal ion in the reagent, and form and be easy to filtering crystal, avoid that difficult filtering problem exists in the subsequent technique, improve the clearance of calcium, magnesium precipitate, and then improved the clearance of calcium, magnesium ion; Can suppress simultaneously the mn ion precipitation and generate, reduce the loss of mn ion.Carry out solid-liquid separation after reacting completely, and then with Ca in the solution
2+, Mg
2+Ion remaval.It removes calcium, magnesium ion mechanism is as follows:
Principal reaction is:
Ca
2++2F
-＝CaF
2↓
Mg
2++2F
-＝MgF
2↓
Side reaction:
Mn
2++2F
-＝MnF
2↓
Ca
2++CO
3 2-＝CaCO
3↓
Mg
2++CO
3 2-＝MgCO
3↓
Mn
2++CO
3 2-＝MnCO
3↓
Wherein, calcium, magnesium ion reaction generate the fluorination precipitation thing in fluorochemical in the complex reagent and the waste water, supercarbonate helps growing up of Calcium Fluoride (Fluorspan), magnesium fluoride precipitation crystal grain, aluminium salt, ferrous salt have flocculation and complexing action to Calcium Fluoride (Fluorspan), magnesium fluoride precipitation crystal grain, and mantoquita is inhibited to the sedimentary formation of manganese.
Aforesaid a kind of complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion, the component of its complex reagent derives from NaF, NH
4HCO
3, NaHCO
3, FeCl
2, Al
2(SO
4)
3, NH
4F, CuCl
2Chemical reagent.
A kind of as mentioned above complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion, its pending Mn-bearing waste water pH value control condition is that the pH value is 5～9.
A kind of as mentioned above complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion, its reagent adding form are that dry powder adds or is mixed with solution and adds.
A kind of as mentioned above complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion, its reagent form of adding are obtain solution when adding, and the massfraction of the shared solution of this complex reagent is 25～40%.
Complex reagent of the present invention possesses following advantage: preparation is simple, and raw material sources are extensive; Be applicable to the Treatment of Wastewater With Manganese of various ionic concns, and applicable pH value scope is wide: 5-9; Have high calcium, magnesium ion clearance, by regulating addition, clearance can reach 100%; Can under guaranteeing that the mn ion rate of loss is less than 0.2% prerequisite, effectively remove calcium, magnesium ion in the former Mn-bearing waste water, reach the purpose of separating calcium, magnesium ion.
The present invention is applicable to the complex reagent that separates calcium, magnesium ion in the Mn-bearing waste water.
Embodiment
A kind of complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion of the present invention, its concrete using method is as follows:
The preparation complex reagent, when adopting dry powder reinforced, the dry powder complex reagent is by joining in the reaction tank by the dry powder feeding machine in the feed bin, or when adopting solution reinforced, is mixed with 25%～40% complex reagent solution, joins in the reaction tank by supply pump.Stir by agitator afterwards, make complex reagent in the pond fully after reaction for some time, overflow enters in the settling tank, through abundant reacted Mn-bearing waste water leaves standstill for some time in settling tank after, produces Ca, Mg throw out.After filtering, filtered liquid enters subsequent disposal, and throw out is recycled processing.
Its specific embodiment has:
Embodiment 1: select NaF for use, NH
4HCO
3, NaHCO
3, FeCl
2, Al
2(SO
4)
3, NH
4F, CuCl
2Chemical reagent preparation complex reagent, component is chosen as: component Na
+Content 34%, component C u
2+Content 4%, component Fe
2+Content 3%, component NH
4 +Content 8%, component Al
3+Content 0.5%, component HCO
3 -Content 21%, component F
-Content 22%, component C l
-Content 7%, component SO
4 2-Content 0.5%.
Employing dry powder is reinforced, complex reagent coefficient of discharge 1.05, and Mn-bearing waste water 10L/h, the pH value is 6.8, water sample starting point concentration: Mn
2+Concentration 4020mg/m
3, Ca
2+Concentration 360mg/m
3, Mg
2+Concentration is 2020mg/m
3Reaction times 1h, precipitation residence time 1h.Under these conditions, Ca
2+Clearance 100%, Mg
2+Clearance 100%.
Embodiment 2: select NaF for use, NH
4HCO
3, NaHCO
3, FeCl
2, Al
2(SO
4)
3, NH
4F, CuCl
2Chemical reagent preparation complex reagent, component is chosen as: component Na
+Content 36%, component C u
2+Content 2%, component Fe
2+Content 1%, component NH
4 +Content 8%, component Al
3+Content 1%, component HCO
3 -Content 22%, component F
-Content 21%, component C l
-Content 8%, component SO
4 2-Content 1%.
Employing solution adds, and complex reagent is mixed with solution with coefficient of discharge 1.0, and massfraction is 25%, Mn-bearing waste water 10L/h, and the pH value is 8.5, water sample starting point concentration: Mn
2+Concentration 4020mg/m
3, Ca
2+Concentration 360mg/m
3, Mg
2+Concentration is 2020mg/m
3Reaction times 1h, precipitation residence time 1h.Under these conditions, Ca
2+Clearance 100%, Mg
2+Clearance 99.3%.
Embodiment 3: select NaF for use, NH
4HCO
3, NaHCO
3, FeCl
2, Al
2(SO
4)
3, NH
4F, CuCl
2Chemical reagent preparation complex reagent, component is chosen as: component Na
+Content 36%, component C u
2+Content 3%, component Fe
2+Content 2%, component NH
4 +Content 8%, component Al
3+Content 0.5%, component HCO
3 -Content 22%, component F
-Content 20%, component C l
-Content 8%, component SO
4 2-Content 0.5%.
Employing dry powder is reinforced, complex reagent coefficient of discharge 1.0, Mn-bearing waste water 1m
3/ h, the pH value is 8.5, water sample starting point concentration: Mn
2+Concentration 4020mg/m
3, Ca
2+Concentration 360mg/m
3, Mg
2+Concentration is 2020mg/m
3Reaction times 1h, precipitation residence time 1h.Under these conditions, Ca
2+Clearance 100%, Mg
2+Clearance 98.7%.
Embodiment 4: select NaF for use, NH
4HCO
3, NaHCO
3, FeCl
2, Al
2(SO
4)
3, NH
4F, CuCl
2Chemical reagent preparation complex reagent, component is chosen as: component Na
+Content 37%, component C u
2+Content 2%, component Fe
2+Content 1%, component NH
4 +Content 8%, component Al
3+Content 0.5%, component HCO
3 -Content 21%, component F-content 22%, component C l
-Content 8%, component SO
4 2-Content 0.5%.
Employing solution adds, and complex reagent is mixed with solution with coefficient of discharge 1.05, and massfraction is 40%, Mn-bearing waste water 1m
3/ h, the pH value is 6.8, water sample starting point concentration: Mn
2+Concentration 4020mg/m
3, Ca
2+Concentration 360mg/m
3, Mg
2+Concentration is 2020mg/m
3Reaction times 1h, precipitation residence time 1h.Under these conditions, Ca
2+Clearance 100%, Mg
2+Clearance 99.8%.
Embodiment 5: select NaF for use, NH
4HCO
3, NaHCO
3, FeCl
2, Al
2(SO
4)
3, NH
4F, CuCl
2Chemical reagent preparation complex reagent, component is chosen as: component Na
+Content 34%, component C u
2+Content 2.5%, component Fe
2+Content 2.5%, component NH
4 +Content 9%, component Al
3+Content 1%, component HCO
3 -Content 23%, component F
-Content 19%, component C l
-Content 8%, component SO
4 2-Content 1%.
Employing dry powder is reinforced, complex reagent coefficient of discharge 1.02, Mn-bearing waste water 20m
3/ h, the pH value is 6.8, water sample starting point concentration: Mn
2+Concentration 4020mg/m
3, Ca
2+Concentration 360mg/m
3, Mg
2+Concentration is 2020mg/m
3Reaction times 1h, precipitation residence time 1h.Under these conditions, Ca
2+Clearance 99.9%, Mg
2+Clearance 97.6%.
Claims (6)
1. complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion is characterized in that comprising following component:
Component Na
+Content 34～39%, component C u
2+Content 2～4%, component Fe
2+Content 1～3%, component NH
4 +Content 8～10%, component Al
3+Content 0.5～1.5%, component HCO
3 -Content 21～24%, component F
-Content 19～22%, component C l
-Content 5～8%, component SO
4 2-Content 0.5～1%.
2. a kind of using method that is used for separating the complex reagent of Mn-bearing waste water calcium, magnesium ion as claimed in claim 1 is to adopt chemical precipitation method, is characterised in that to add by NaF NH in Mn-bearing waste water
4HCO
3, NaHCO
3, FeCl
2, Al
2(SO
4)
3, NH
4F, CuCl
2The complex reagent of chemical reagent preparation carries out solid-liquid separation after reacting completely.
3. a kind of complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion as claimed in claim 1, its using method are characterised in that the reagent addition is 1.0～1.05 times of theoretical required addition.
4. a kind of complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion as claimed in claim 1, its using method are characterised in that pending Mn-bearing waste water pH value control condition is that the pH value is 5～9.
5. a kind of complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion as claimed in claim 1, its using method are characterised in that complex reagent adding form is that dry powder adds.
6. a kind of complex reagent that is used for separating Mn-bearing waste water calcium, magnesium ion as claimed in claim 4, its using method are characterised in that complex reagent is that obtain solution adds, and the massfraction of the shared solution of this complex reagent is 25～40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101431152A CN102276070A (en) | 2011-05-27 | 2011-05-27 | Composite reagent for separating calcium ions and magnesium ions from manganiferous waste water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101431152A CN102276070A (en) | 2011-05-27 | 2011-05-27 | Composite reagent for separating calcium ions and magnesium ions from manganiferous waste water |
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|---|---|
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ID=45101870
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351048A (en) * | 2012-11-22 | 2013-10-16 | 中节能六合天融环保科技有限公司 | Organic composite reagent for removing calcium ions in manganese-containing wastewater |
| CN111876600A (en) * | 2020-08-07 | 2020-11-03 | 贵州中伟资源循环产业发展有限公司 | Method for removing calcium and magnesium ions in sulfate solution and sulfate solution |
| CN112786988A (en) * | 2020-11-26 | 2021-05-11 | 清华四川能源互联网研究院 | Impurity removal and treatment method in lithium battery scrapped positive electrode material recovery process |
-
2011
- 2011-05-27 CN CN2011101431152A patent/CN102276070A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351048A (en) * | 2012-11-22 | 2013-10-16 | 中节能六合天融环保科技有限公司 | Organic composite reagent for removing calcium ions in manganese-containing wastewater |
| CN111876600A (en) * | 2020-08-07 | 2020-11-03 | 贵州中伟资源循环产业发展有限公司 | Method for removing calcium and magnesium ions in sulfate solution and sulfate solution |
| CN112786988A (en) * | 2020-11-26 | 2021-05-11 | 清华四川能源互联网研究院 | Impurity removal and treatment method in lithium battery scrapped positive electrode material recovery process |
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Application publication date: 20111214 |