CN104083845A - Method for stabilizing water-soluble manganese ions in manganese ore leaching residue - Google Patents
Method for stabilizing water-soluble manganese ions in manganese ore leaching residue Download PDFInfo
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- CN104083845A CN104083845A CN201410329303.8A CN201410329303A CN104083845A CN 104083845 A CN104083845 A CN 104083845A CN 201410329303 A CN201410329303 A CN 201410329303A CN 104083845 A CN104083845 A CN 104083845A
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- manganese
- manganese ore
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- leaching residue
- ore leaching
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Abstract
The invention provides a method for stabilizing water-soluble manganese ions in manganese ore leaching residue. The method comprises the following basis steps: mixing and pulping the manganese ore leaching residue and water in a liquid-solid ratio of 2:1 to 6:1, adjusting the pH value of the slurry to be 7 to 10 by saturated whitewash, adding sodium silicate in the mass ratio to the manganese ore leaching residue of 2 to 5 percent, stirring for reacting for 5 to 60 minutes at the temperature of 25 to 60 DEG C, and after the reaction is completed, filtering the mixture till the solidification rate of Mn<2+> in the manganese ore leaching residue reaches more than 98 percent and reaches the grade-A discharging concentration standard in identification for extraction toxicity (GB5085.3-2007) and the integrated sewage discharging standard (GB8978-96). The method has the advantages that the process flow is simple; by a wet-method mixing way, the uniform mixing of a curing agent and the manganese ore leaching residue can be realized, the consumption of the curing agent can be greatly reduced, and the treatment cost is low.
Description
Technical field:
The present invention relates to a kind of method that manganese ore soaks slag stabilization processes, be particularly suitable for adopting under alkali condition silicate solidify manganese ore soak slag in water-soluble manganese ion, belong to industrial solid castoff integrated treatment field.
Background technology:
It is in manganese product production process, to utilize the filtration waste residue producing after acidleach manganese ore powder that manganese ore soaks slag, and outward appearance is black scattered paste shape, is block after air-dry.At present, China's manganese slag burden has exceeded 100,000,000 t.Manganese ore soaks slag and generally adopts the simple and easy disposal of outdoor mode of storing up of building a dam, due to the reason such as the control measures such as antiseep are undesirable, drench and soak through rainwater, produce diffusate, wherein major pollutants manganese ion is dense, surface water to enterprise's periphery, underground water, bed mud in river, soil cause severe contamination, and harm resident's is healthy, destroy the ecosystem.Excessive Manganese element can make that people's liver function damage, enteron aisle is smooth, nervous system dysfunction.The phenomenon that one Ge Meng manufacturing enterprise pollutes river, pollute a slice soil is still comparatively general, and what have has even led to serious Disputes of Environmental Pollution.Reduce to greatest extent the harm that manganese ore soaks slag, extremely urgent.
At present, the approach that manganese ore is soaked to slag recycling has a lot, comprises the extraction of the valuable elements such as manganese, ammonia, silicon, aluminium, iron, nickel, cobalt, chromium, obtains corresponding compound, but these class methods often technique is loaded down with trivial details, cost is high, practical value is little; Also there is the silicate sturcture that utilizes high-load in manganese slag, be applied in construction material aspect, as cement, steam-pressing brisk, ceramic material, insulation material etc., such processing method part has realized industrialization, but because the sulphates content of manganese slag own is larger, contain contents of many kinds of heavy metal ion, and do not possess hydration activity and gelation, thereby use amount is few; In agricultural, utilize manganese ore to soak to contain the necessary tens of kinds of elements of plant growth in slag and compound is made chemical fertilizer, but do not resolve the problem of solidification of heavy metal ion in manganese slag, if absorbed by crops, plurality of heavy metal ion will enrichment in human body, unhealthful.From the recycling approach of manganese slag, because utilization is too low, the effective not high reason of technology cannot obtain practical application.Therefore, manganese slag application technology as the second resource can not solve pollution of Mn dregs problem present stage.Using for reference stabilization of dangerous waste materials/curing technology method, manganese slag is carried out to harmless treatment, ensure the environmental safety of manganese slag, is that a kind of manganese slag is processed new approaches.
Soak slag in order to solidify preferably processing manganese ore, people have found out many methods, as open source literature has been reported the document that some are relevant, take passages as follows through retrieval:
1. [autograph] a kind of Innocent treatment method of electrolytic manganese slag [author] Wang Jiwei, Zhou Changbo, Du Bing etc. [mechanism] China Environmental Science Research Institute's cleaner production center [periodical name] environmental project journal, 2014,8 (1): 329-333[digest] utilize the medicament of quick lime as harmless treatment, proportioning is electrolytic manganese residues: quick lime=8: 1, in the time adding 12.5g quick lime or 3g NaOH in 100g electrolytic manganese residues, the effect of solidifying manganese reaches 99%, can reach discharging standards.
2. [application (patent) number] CN102161048A[title] a kind of Innocent treatment method of electrolytic manganese slag [application (patent right) people] Chinese Research Academy of Environmental Sciences.The method is by first electrolytic manganese residues Mechanical Crushing, pour into and in mixer, add pulverized limestone and water, and add a certain amount of silicates additive to serve as dispersant, stir 3～5min, discharging adds a certain amount of water-soluble resin Sulfonates additive and iron chloride to stir 3～5min after shifting second mixer, discharging is transferred to the 3rd mixer and fully stirs 3～5min, and drying control moisture content carries out landfill disposal after 16%, and whole process is carried out Ammonia recovery.Its radioactivity of electrolytic manganese residues and toxicity are all within safe range after treatment.
3. [application (patent) number] CN102794291A[title] stabilization processes [application (patent right) people] China Environmental Science Research Institute of soluble manganese ion and soluble state selenium in a kind of electrolytic manganese residues.The method is by first broken, dispersion, dry of electrolytic manganese residues, after adding triethanolamine, carry out ball milling 3～5min, add aluminium oxide, after stirring, repeatedly add clear water to stir 3～5min, continue to add copperas solution to stir 1～2min, continue to add pulverized limestone, after stirring, repeatedly add clear water to continue to stir 2～3min and obtain being dried processing after material.Leachate can reach the standard of integrated wastewater discharge standard and hazardous waste leaching characteristic identification.
4. [application (patent) number] CN103286116A[title] a kind of method [application (patent right) people] University Of Chongqing of harmless treatment electrolytic manganese residues.The method is that fresh electrolytic manganese residues is put into mixer, the sodium phosphate that to add with electrolytic manganese residues mass ratio in stirring be 3%～5%, after stirring, continue to add with electrolytic manganese residues mass ratio the pulverized limestone that is 5%～10%, till being stirred to and emitting without ammonia, obtaining material is innoxious electrolytic manganese residues.
5. [application (patent) number] CN103320621A[title] method [application (patent right) people] Central South University of heavy metal coproduction sulphur in a kind of curing electrolytic manganese residues.The method is to obtain Containing Sulfur calcium calcining by mix then roasting 1.5～2h at 800～1000 DEG C containing calcium sulfite and the raw material of calcium carbonate and the ratio of carbon based reductive 1: 2 in molar ratio～3 row, by cross the electrolytic manganese residues of 50～400 mesh sieves and Containing Sulfur calcium calcining by butt than 3～8: 1 mixes, and to add water to make the ratio of power and water solution manganese slag be 4～6: 1, filter residue and filtrate that stirring at room temperature 4～6h filters, filter residue is the manganese slag after solidifying, after the static 24～48h of filtrate, separate out sulphur, filtrate cycle.
Recognize from above-mentioned result for retrieval, open source literature introduction mainly: 1. document adopts calcium oxide or NaOH to solidify manganese slag, and treatment effect is good, but hardener dose is larger, and residue alkalescence is large, is unfavorable for outer row; 2. document adopts calcium oxide alkalization, and silicate disperses, water-soluble resin Sulfonates additive aquation, and the steps such as iron chloride oxidation reclaim ammonia, solidify manganese, and manganese is can not acid-soluble tetravalence manganese ion form existing, but this method long flow path, complex process, cost is high; 3. document adopts oxidation divalent manganesetion, and selenite and iron content, aluminum oxide form the curing manganese slag of method of slightly solubility complex, and flow process is complicated, high cost, and ball milling has increased energy consumption; 4. document solidifies water-soluble manganese in manganese slag by adding calcium oxide and sodium phosphate, and process is simple, but adopts sodium phosphate and ammonia, manganese to form double salt, under acid condition, can discharge ammonia radical ion, affects solidification effect; 5. document adopts the solid manganese desulfurization of high-temperature roasting, and high temperature a large amount of coal that need burn provides heat, has increased energy consumption, and has inevitably produced a large amount of coal-fired flue-gas, causes atmosphere pollution.
To sum up, the curing process of existing bibliographical information, cost is generally higher, and the use of Part Methods will bring secondary pollution.Therefore the manganese of, selecting the curing manganese ore of method of a kind of economy, environmental protection to soak in slag has great importance.
Summary of the invention:
The object of this invention is to provide a kind of efficient, environmental protection, economic method is solidified manganese ore and is soaked water-soluble manganese ion and heavy metal ion in slag.It is characterized in that utilizing sodium metasilicate is main curing agent, and water-soluble manganese and other heavy metal ion that manganese ore is soaked in slag can fully be reacted the indissoluble silicate compound that generates stable chemical nature with sodium metasilicate.
Above-mentioned said manganese ore soaks the industrial residue that slag refers to that manganese ore is discharged after manganese is carried in acidleach in manganese product production process, and this waste residue is faintly acid, and complicated component contains a certain amount of water-soluble divalent manganesetion.
Above-mentioned said sodium metasilicate mainly serves as curing agent effect in manganese ion stabilization processes process, and principle is in alkaline environment, and silicate and manganese ion form the manganous silicate of stable chemical nature, indissoluble.
The present invention realizes like this, manganese ore is soaked to slag and within 2: 1～6: 1, mix making beating with water with liquid-solid ratio, slurry pH is adjusted to 7～10 with saturated limewater, add that to soak slag mass ratio with manganese ore be 2%～5% sodium metasilicate, at 25 DEG C～60 DEG C stirring reaction 5～60min, after having reacted, after filtration, manganese ore soaks Mn in slag
2+curing degree reaches more than 98%, reaches the first grade discharging concentration standard in GB5085.3-2007 leaching characteristic identification and GB8978-96 " sewage comprehensive draining standard ".
Compared with the present invention soaks slag harmlessness treatment technology with existing manganese ore, its outstanding substantive distinguishing features and significant progress are:
(1) this method adopts disposable processing manganese ore to soak slag, and technical process is simple, and processing cost is cheaper;
(2) this method adopts the mode of wet-mixing, and the even mixed problem that can solve curing agent and manganese ore and soak slag has greatly reduced the use amount of curing agent.Manganese ore after sodium metasilicate solidifies soaks slag, Mn
2+curing degree reaches more than 98%; Manganese ore after treatment soaks the Leaching inspection of slag, and its manganese and lead content are lower than the limit value (Mn≤2.0mg/L, Pb≤1.0mg/L) of leaching toxicity from solid waste standard (GB8978-96).
Detailed description of the invention:
Embodiment 1
Manganese ore is soaked to slag and water is uniformly mixed by liquid-solid ratio at 2: 1, with after saturated limewater regulator solution pH to 10, adding manganese ore to soak slag mass ratio is 3% sodium metasilicate, at 25 DEG C of stirring reaction 60min.Reaction finishes rear filtration, and filtrate cycle is used.Manganese ore soaks Mn in slag
2+curing degree reaches 98.7%.Manganese ore after treatment soaks slag to be checked through Leaching, and its manganese and lead content are lower than the limit value (Mn≤2.0mg/L, Pb≤1.0mg/L) of leaching toxicity from solid waste standard (GB8978-96).
Table 1 manganese ore soaks slag main component
Embodiment 2
Manganese ore is soaked to slag and water is uniformly mixed by liquid-solid ratio at 3: 1, with after saturated limewater regulator solution pH to 8, adding manganese ore to soak slag mass ratio is 5% sodium metasilicate, at 35 DEG C of stirring reaction 5min.Reaction finishes rear filtration, and filtrate cycle is used.Manganese ore soaks Mn in slag
2+curing degree reaches 99.9%.Manganese ore after treatment soaks slag to be checked through Leaching, and its manganese and lead content are lower than the limit value (Mn≤2.0mg/L, Pb≤1.0mg/L) of leaching toxicity from solid waste standard (GB8978-96).
Embodiment 3
Manganese ore is soaked to slag and water is uniformly mixed by liquid-solid ratio at 5: 1, with after saturated limewater regulator solution pH to 9, adding manganese ore to soak slag mass ratio is 2% sodium metasilicate, at 45 DEG C of stirring reaction 35min.Reaction finishes rear filtration, and filtrate cycle is used.Manganese ore soaks Mn in slag
2+curing degree reaches 98.1%.Manganese ore after treatment soaks slag to be checked through Leaching, and its manganese and lead content are lower than the limit value (Mn≤2.0mg/L, Pb≤1.0mg/L) of leaching toxicity from solid waste standard (GB8978-96).
Embodiment 4
Manganese ore is soaked to slag and water is uniformly mixed by liquid-solid ratio at 6: 1, with after saturated limewater regulator solution pH to 7, adding manganese ore to soak slag mass ratio is 4% sodium metasilicate, at 60 DEG C of stirring reaction 20min.Reaction finishes rear filtration, and filtrate cycle is used.Manganese ore soaks Mn in slag
2+curing degree reaches 99.1%.Manganese ore after treatment soaks slag to be checked through Leaching, and its manganese and lead content are lower than the limit value (Mn≤2.0mg/L, Pb≤1.0mg/L) of leaching toxicity from solid waste standard (GB8978-96).
Several harmless treatment reagent cost of table 2 comparison (unit)
From above-mentioned each example, can find out, the concentration of soaking manganese in slag leachate by manganese ore after sodium metasilicate and calcium oxide Combined Treatment all can reach the first grade discharging concentration standard in GB5085.3-2007 leaching characteristic identification and GB8978-96 " sewage comprehensive draining standard ".In table 2, be the processing cost comparison of the innoxious additive of various differences in other documents, adopt as seen sodium metasilicate processing cost lower, be convenient to that the method is industrialized to be applied.
Claims (1)
1. a manganese ore soaks the method for water-soluble manganese ion stabilization processes in slag, it is characterized in that soaking and in slag, adding water at manganese ore, the liquid-solid ratio that regulates water and manganese ore to soak slag is 2: 1～6: 1 rear stirring to pulps, after slurry pH value being adjusted to 7～10 with saturated limewater, add manganese ore to soak the sodium metasilicate of slag amount 2%～5%, stirring reaction 5～60min at the temperature of 25 DEG C～60 DEG C, after having reacted, after filtration, filtrate is transmitted back to pulping process and recycles, and manganese ore soaks the curing degree of water-soluble manganese in slag and reaches more than 98%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262336A (en) * | 2018-02-24 | 2018-07-10 | 昆明理工大学 | A kind of solidification processing method of electrolytic manganese residues |
| CN110052489A (en) * | 2019-04-16 | 2019-07-26 | 北京净界新宇环保科技有限公司 | A kind for the treatment of agent and preparation method for manganese mud heavy metal pollution |
| CN110668466A (en) * | 2019-11-05 | 2020-01-10 | 党海哲 | Harmless treatment method for electrolytic manganese slag |
| CN112792086A (en) * | 2019-11-14 | 2021-05-14 | 西南科技大学 | Method for harmless treatment of electric field reinforced electrolytic manganese slag |
| CN114436622A (en) * | 2022-03-23 | 2022-05-06 | 湖南省交通科学研究院有限公司 | Subgrade filling material based on manganese tailing slag and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262336A (en) * | 2018-02-24 | 2018-07-10 | 昆明理工大学 | A kind of solidification processing method of electrolytic manganese residues |
| CN110052489A (en) * | 2019-04-16 | 2019-07-26 | 北京净界新宇环保科技有限公司 | A kind for the treatment of agent and preparation method for manganese mud heavy metal pollution |
| CN110668466A (en) * | 2019-11-05 | 2020-01-10 | 党海哲 | Harmless treatment method for electrolytic manganese slag |
| CN110668466B (en) * | 2019-11-05 | 2023-09-15 | 党海哲 | Harmless treatment method for electrolytic manganese slag |
| CN112792086A (en) * | 2019-11-14 | 2021-05-14 | 西南科技大学 | Method for harmless treatment of electric field reinforced electrolytic manganese slag |
| CN114436622A (en) * | 2022-03-23 | 2022-05-06 | 湖南省交通科学研究院有限公司 | Subgrade filling material based on manganese tailing slag and preparation method and application thereof |
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Application publication date: 20141008 |