CN102795641B - Novel method for direct extraction recovery of ammonia nitrogen from electrolyzed manganese slag - Google Patents
Novel method for direct extraction recovery of ammonia nitrogen from electrolyzed manganese slag Download PDFInfo
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- CN102795641B CN102795641B CN201210301899.1A CN201210301899A CN102795641B CN 102795641 B CN102795641 B CN 102795641B CN 201210301899 A CN201210301899 A CN 201210301899A CN 102795641 B CN102795641 B CN 102795641B
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Abstract
The invention discloses a novel method for direct extraction recovery of ammonia nitrogen from electrolyzed manganese slag. The novel method comprises the following steps of directly adding an alkaline preparation and a foaming agent into fresh manganese slag subjected to crushing, dispersion, drying and ball-milling so that a pH value and humidity in an electrolyzed manganese slag environment are changed and transformation of NH4<+> from a solid phase, a liquid phase into a gas phase is promoted, and introducing released NH3 gas into a multistage absorption device by a negative-pressure suction device cover located above a mixer so that the released NH3 gas is absorbed by water or dilute sulphuric acid and then is transformed into ammonia water or ammonium sulfate. The novel method for direct extraction recovery of ammonia nitrogen from electrolyzed manganese slag solves the problem that the existing extraction recovery methods have high water consumption, high energy consumption and complex processes, greatly reduces environmental pollution hidden troubles of ammonia nitrogen in manganese slag, and realizes extraction and utilization of an ammonia nitrogen resource well.
Description
Technical field
The present invention relates to resource circulation utilization technical field, particularly relate to a kind of method of extracting directly recovery ammonia nitrogen from electrolytic manganese residues.
Background technology
Manganese is grand strategy and the basic substance of national economy, has very important strategic position in national economy.Due to Chinese society rapid development of economy, increasing to the demand of electrolytic manganese, China's electrolytic manganese industry have also been obtained development at a high speed.At present, electrolytic manganese is the second largest industry of China's ferrous metallurgy.By the end of the year 2007, electrolytic manganese enterprise of China will add up to throughput to reach 1,780,000 tons, actual output 1,020,000 tons, and more than 97% of production capacity and the actual output Jun Zhan world, becomes electrolytic manganese production maximum in the world, consumption and export State.
But electrolytic manganese industry is typical " high investment, high flow rate, high pollution, poor benefit " " three high and one low " industry, while its high speed development, shortage of resources, problem of environmental pollution also highlight day by day, and wherein electrolytic manganese residues pollutes and seems particularly outstanding.Electrolytic manganese residues produces electrolytic metal Mn and the industrial residue that discharges, be manganous carbonate breeze after sulfuric acid leaching again through residue that press filtration solid-liquid separation produces.Due to production technique, in electrolytic manganese residues containing in a large number with ionic state NH+4 for main memory ammonia nitrogen, after measured, in dry slag, ammonia-nitrogen content is 6000-8000mg/kg.
Electrolytic manganese residues is mainly to stack both at home and abroad at present, and stacking place construction is also lack of standardization, causes serious pollution to environment.Ammonia nitrogen in manganese slag is once under the effect that drenches with rain at weathering, from slag, migration is discharged in the soil of periphery and earth's surface, underground water, will cause body eutrophication, and then cause algal bloom in water surrounding, consume oxygen in water, affect the growth and breeding of fish; Algae produces toxin in process of growth, and water quality of river will be caused to decline, and causes a series of serious harms such as waterworks paralysis.In recent years due to the lasting reduction of ore grade, be reduced between 10 ~ 12% by more than 20%, often produce 1 ton of electrolytic metal Mn and rise to generation 9 ~ 11 tons of waste residues from generation 6 ~ 8 tons of waste residues started, and contain multiple pollutant in waste residue, moiety concentrations is high.The extraction recovery technology of ammonia nitrogen in electrolytic manganese residues, not only can greatly reduce the environmental pollution hidden danger of ammonia nitrogen in manganese slag, and can realize the extraction and application of ammonia nitrogen resource, meet the Development patterns of Sustainable development.
There is some scholars to be studied the recovery of ammonia nitrogen in manganese slag, be generally adopt round-about way, i.e. liquid phase dissolved method of enrichment: electrolytic manganese residues is soluble in water, then filtrate heated, isolation and identification obtains ammoniacal liquor.But this method water consumption is large, energy consumption is high and complex process.The Tao Changyuan of University Of Chongqing etc. have studied the method utilizing clear water washery slag-aluminium salt precipitation method to reclaim ammonia nitrogen from electrolytic manganese residues, inquire into the impact of the conditions such as precipitation agent dosage, temperature of reaction for the ammonia nitrogen rate of recovery, reclaim ammonia nitrogen under its top condition and can reach more than 95%, achieve good achievement, but its removal process needs to be warming up to 95 DEG C, reaction times needs 2 hours, and treatment agent price is higher, from cost or technique is all unfavorable for the practical application of this technology, real industrial applications also has very long stretch to walk.The people such as the Yu Hongbing of Nankai University utilize distilled water to extract for ammonia nitrogen in ammonia nitrogen slag, its extraction yield can reach more than 60%, but has more impurity due in the mixed solution that produces after washery slag, is difficult to direct reuse, simultaneous reactions condition is comparatively harsh, and technology is also in the exploratory stage.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of method of extracting directly recovery ammonia nitrogen from electrolytic manganese waste residue,
The object of the present invention is to provide a kind of method of extracting directly recovery ammonia nitrogen from electrolytic manganese waste residue, this method overcomes the deficiency of other processing methodes, the environmental pollution hidden danger of ammonia nitrogen in electrolytic manganese residues can be reduced, and the extraction and application of ammonia nitrogen resource can be realized better.
Technical scheme provided by the invention is:
From electrolytic manganese waste residue, extracting directly reclaims a method for ammonia nitrogen, comprises the following steps:
Step one, the electrolytic manganese residues just discharged is obtained material I through broken, dispersion, drying;
Step 2, the material I obtained is carried out ball milling, add trolamine after running 2-3min, add-on is the 0.5-1% of material I quality.Continue to run 3-5min, obtain material II;
Step 3, material II is joined in stirrer, add the calcium lime powder of material II quality 5-10%, stir;
Step 4, in stirrer operational process, slowly add clear water several times, control to add water and mixture mass ratio is stop adding water after 40-50%;
First add the aluminium powder of material II quality 1-2% in step 5, stirrer, then add the calcium lime powder of material II quality 3-5%, continue to stir; The aluminium powder trade mark is FLQ1, FLQ2 or FLQ3, granularity 0.08 ~ 0.10mm.
Step 6, a large amount of ammonia will be produced in whipping process, and by the negative pressure air-suction device cover above stirrer, make negative pressure value reach 60KPa, the ammonia collected will be derived;
Step 7, import in multistage absorption device by ammonia, wherein absorption liquid is the ammoniacal liquor that Water Sproading ammonia obtains that massfraction is 10-15%; Absorption liquid is the dilution heat of sulfuric acid of 25-30%, reclaims ammonia and obtains the ammoniumsulphate soln that massfraction is 5.5-7.5%.
Preferably, in the described a kind of method based on extracting directly recovery ammonia nitrogen from electrolytic manganese residues, in ball milling, add trolamine in step 2 in process as grinding aid, add-on is the 0.5-1% of material I quality.
Preferably, in the described a kind of method based on extracting directly recovery ammonia nitrogen from electrolytic manganese residues, in step 3, step 5, calcium lime powder is added, Ca (OH) 2 is produced through digestion, make the pH value of manganese slag environment be elevated to more than 11, and as whipping agent, produce ammonia.
Preferably, in the described a kind of method based on extracting directly recovery ammonia nitrogen from electrolytic manganese residues, following requirement is had: calcium lime powder fineness requirement passes through the screen over-size of 120 mesh sieve not higher than 5%, and the content of free calcium oxide is not less than 85% to the calcium lime powder used.
Preferably, in the described a kind of method based on extracting directly recovery ammonia nitrogen from electrolytic manganese residues, add the aluminium powder of material II quality 1-2% in step 5, the aluminium powder trade mark is FLQ1, FLQ2 or FLQ3, granularity 0.08 ~ 0.10mm.
Preferably, in the described a kind of method based on extracting directly recovery ammonia nitrogen from electrolytic manganese residues, in step 6, negative pressure air-suction device cover is installed above stirrer, makes negative pressure value reach 60KPa, derive ammonia.
Preferably, in the described a kind of method based on extracting directly recovery ammonia nitrogen from electrolytic manganese residues, gas is imported in multistage absorption device in step 7, reclaim ammonia when absorption liquid is water and obtain the ammoniacal liquor that massfraction is 10-15%; Reclaiming ammonia when absorption liquid is the dilution heat of sulfuric acid of 25-30%, to obtain massfraction be that the ammonium sulfate of 5.5-7.5% is molten.
Accompanying drawing explanation
Fig. 1 is the process flow diagram reclaiming ammonia nitrogen for extracting directly from electrolytic manganese waste residue of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art:
Step one, the electrolytic manganese residues just discharged is obtained material I through broken, dispersion, drying.
Step 2, the material I obtained is carried out ball milling, after running 2-3min, add trolamine, continue to run 3-5min, obtain material II.
Step 3, material II is joined in stirrer, add the calcium lime powder of material II quality 5-10%, stir; Following requirement is had: calcium lime powder fineness requirement passes through the screen over-size of 120 mesh sieve not higher than 5%, and the content of free calcium oxide is not less than 85% to the calcium lime powder used.
Step 4, in stirrer operational process, slowly add clear water several times, control to add water and mixture mass ratio is stop adding water after 40-50%.
First add the aluminium powder of material II quality 1-2% in step 5, stirrer, then add the calcium lime powder of material II quality 3-5%, continue to stir; The aluminium powder trade mark is FLQ1, FLQ2 or FLQ3, granularity 0.08 ~ 0.10mm.
Step 6, a large amount of ammonia will be produced in whipping process, and by the negative pressure air-suction device cover above stirrer, make negative pressure value reach 60KPa, the ammonia collected will be derived.
Step 7, import in multistage absorption device by ammonia, wherein absorption liquid is the ammoniacal liquor that Water Sproading ammonia obtains that massfraction is 10-15%; Absorption liquid is the dilution heat of sulfuric acid of 25-30%, reclaims ammonia and obtains the ammoniumsulphate soln that massfraction is 5.5-7.5%.
Claims (5)
1. from electrolytic manganese residues, extracting directly reclaims a method for ammonia nitrogen, wherein, comprises the following steps:
Step one, the electrolytic manganese residues just discharged is obtained material I through broken, dispersion, drying;
Step 2, the material I obtained is carried out ball milling, after running 2-3min, add trolamine, continue to run 3-5min, obtain material II;
Step 3, material II is joined in stirrer, add the calcium lime powder of material II quality 5-10%, stir;
Step 4, in stirrer operational process, slowly add clear water several times, control to add water and mixture mass ratio is stop adding water after 40-50%;
First add the aluminium powder of material II quality 1-2% in step 5, stirrer, then add the calcium lime powder of material II quality 3-5%, continue to stir;
Step 6, will ammonia be produced in whipping process, by the negative pressure air-suction device cover above stirrer, the ammonia collected be derived;
Step 7, import in multistage absorption device by ammonia, wherein absorption liquid is water or dilution heat of sulfuric acid, reclaims ammonia and obtains ammoniacal liquor or ammoniumsulphate soln;
Wherein, in step 3, step 5, add calcium lime powder, produce Ca (OH) through digestion
2, make the pH value of manganese slag environment be elevated to more than 11, and as whipping agent, produce ammonia,
The aluminium powder of material II quality 1-2% is added, granularity 0.08 ~ 0.10mm in step 5.
2. the method for claim 1, is characterized in that: in ball milling, add trolamine in step 2 in process as grinding aid, add-on is the 0.5-1% of material I quality.
3. the method for claim 1, is characterized in that: have following requirement to the calcium lime powder used: calcium lime powder fineness requirement passes through the screen over-size of 120 mesh sieve not higher than 5%, and the content of free calcium oxide is not less than 85%.
4. the method for claim 1, is characterized in that: install negative pressure air-suction device cover above stirrer in step 6, makes negative pressure value reach 60KPa, derives ammonia.
5. the method for claim 1, is characterized in that: imported by gas in multistage absorption device in step 7, reclaims ammonia and obtain the ammoniacal liquor that massfraction is 10-15% when absorption liquid is water; Reclaim ammonia when absorption liquid is the dilution heat of sulfuric acid of 25-30% and obtain the ammoniumsulphate soln that massfraction is 5.5-7.5%.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103570155B (en) * | 2013-10-16 | 2015-04-01 | 江苏晨力环保科技有限公司 | Manganese slag percolation wastewater treatment system and treatment method thereof |
| CN103817132B (en) * | 2013-12-13 | 2016-08-24 | 中国环境科学研究院 | A kind of electrolytic manganese residues processing system |
| CN104529196B (en) * | 2014-12-10 | 2017-01-11 | 北京科技大学 | Method for extracting ammonium and modifying electrolytic manganese residue |
| CN104891530B (en) * | 2015-05-18 | 2017-06-16 | 贵州省化工研究院 | A kind of method that ammonium root is reclaimed in electrolytic manganese residues |
| CN106927507B (en) * | 2017-03-29 | 2018-05-22 | 湘潭市环境保护科学研究院 | A kind of electrolysis MnO2With the method that waste residue containing Mn prepares manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer in electrolysis Mn productions |
| CN109503045A (en) * | 2019-01-24 | 2019-03-22 | 中国恩菲工程技术有限公司 | The method for carrying out mine worked-out section filling using electrolytic manganese residues |
| CN114405962A (en) * | 2021-12-28 | 2022-04-29 | 武汉大学(肇庆)资源与环境技术研究院 | Method for efficiently removing ammonia nitrogen in electrolytic manganese slag |
| CN115382886B (en) * | 2022-08-10 | 2023-06-20 | 桂林理工大学 | Mechanical homogenization-low-temperature thermal activation accurate harmless treatment method for electrolytic manganese slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101864823A (en) * | 2010-06-10 | 2010-10-20 | 湖北声荣环保节能科技有限公司 | Aerated concrete building block produced by heavy metal-removed manganese carbonate tailing and manufacturing method thereof |
| CN102161048A (en) * | 2011-01-06 | 2011-08-24 | 中国环境科学研究院 | Innocent treatment method of electrolytic manganese slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101864823A (en) * | 2010-06-10 | 2010-10-20 | 湖北声荣环保节能科技有限公司 | Aerated concrete building block produced by heavy metal-removed manganese carbonate tailing and manufacturing method thereof |
| CN102161048A (en) * | 2011-01-06 | 2011-08-24 | 中国环境科学研究院 | Innocent treatment method of electrolytic manganese slag |
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