CN102795641A - 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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- CN102795641A CN102795641A CN2012103018991A CN201210301899A CN102795641A CN 102795641 A CN102795641 A CN 102795641A CN 2012103018991 A CN2012103018991 A CN 2012103018991A CN 201210301899 A CN201210301899 A CN 201210301899A CN 102795641 A CN102795641 A CN 102795641A
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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 a solid phase and 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 the resource circulation utilization technical field, relate in particular to a kind of method that reclaims ammonia nitrogen of from electrolytic manganese residues, directly extracting.
Background technology
Manganese is the grand strategy and the basic substance of national economy, in national economy, has crucial strategic position.Because the Chinese society rapid development of economy, increasing to the demand of electrolytic manganese, China's electrolytic manganese industry has also obtained the high speed development.At present, electrolytic manganese is the second largest industry of China's ferrous metallurgy.By the end of the year 2007, China electrolytic manganese enterprise adds up to throughput to reach 1,780,000 tons, 1,020,000 tons of actual outputs, and production capacity and actual output all account for more than 97% of the world, become maximum in the world electrolytic manganese production, consumption and export State.
But the electrolytic manganese industry is typical " high investment, high flow rate, high pollution, poor benefit " " three high one is a low " industry; In 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 is to produce electrolytic metal Mn and the industrial residue that discharges, is the residue that produces through the press filtration solid-liquid separation again after the manganous carbonate breeze leaches through sulfuric acid.Because production technique, contain in the electrolytic manganese residues in a large number with ionic state NH+4 be main memory ammonia nitrogen, through measuring, ammonia-nitrogen content is 6000-8000mg/kg in the dried slag.
At present both at home and abroad electrolytic manganese residues mainly is to be main with stacking, and it is also lack of standardization to stack the place construction, has caused serious pollution to environment.Ammonia nitrogen in the manganese slag is in case under the effect that natural weathering drenches with rain; Migration is discharged in soil and the face of land, the underground water of periphery from slag, will cause body eutrophication, and then cause algal bloom in the water surrounding; Consume oxygen in water, influence the growth and breeding of fish; Algae produces toxin in process of growth, will cause water quality of river to descend, and causes a series of serious harms such as waterworks paralysis.In recent years because the lasting reduction of ore grade; By being reduced between 10～12% more than 20%; 1 ton of electrolytic metal Mn of every production rises to 9～11 tons of waste residues of generation from 6～8 tons of waste residues of generation of beginning, and contains multiple pollutent in the waste residue, the part very high concentrations.The extraction recovery technology of ammonia nitrogen in the electrolytic manganese residues not only can significantly reduce the environmental pollution hidden danger of ammonia nitrogen in the manganese slag, and can realize the extraction and application of ammonia nitrogen resource, meets the Development patterns of Sustainable development.
Having the part scholar that the recovery of ammonia nitrogen in the manganese slag is studied, generally is to adopt round-about way, i.e. liquid phase dissolved method of enrichment: electrolytic manganese residues is soluble in water, then filtrating is heated, is separated and concentrate obtaining ammoniacal liquor.But this method water consumption is big, energy consumption is high and complex process.The Tao Changyuan of University Of Chongqing etc. has studied the method for utilizing clear water washery slag-aluminium salt precipitation method from electrolytic manganese residues, to reclaim ammonia nitrogen; Inquired into of the influence of conditions such as precipitation agent dosage, temperature of reaction for the ammonia nitrogen recovery; Its top condition recover ammonia nitrogen can reach more than 95%, has obtained good achievement, but its removal process need be warming up to 95 ℃; Reaction times needs 2 hours; And the treatment agent price is higher, on cost still is technology, all is unfavorable for the practical application that this is technological, and real industrial applications also has very long stretch to walk.People such as the Yu Hongbing of Nankai University utilize zero(ppm) water to extract for ammonia nitrogen in the ammonia nitrogen slag; Its extraction yield can reach more than 60%, but owing in the mixed solution that produces behind the washery slag more impurity is arranged, is difficult to direct reuse; Reaction conditions is comparatively harsh simultaneously, and technology also is in the exploratory stage.
Summary of the invention
To above-mentioned technical problem, the present invention provides a kind of method that reclaims ammonia nitrogen of from electrolytic manganese waste residue, directly extracting,
The object of the present invention is to provide a kind of method that reclaims ammonia nitrogen of from electrolytic manganese waste residue, directly extracting; This method has overcome the deficiency of other process methodes; The environmental pollution hidden danger of ammonia nitrogen in the 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:
A kind of method that reclaims ammonia nitrogen of from electrolytic manganese waste residue, directly extracting may further comprise the steps:
Step 1, the electrolytic manganese residues that will just discharge obtain material I through fragmentation, dispersion, drying;
Step 2, the material I that obtains is carried out ball milling, add trolamine behind the operation 2-3min, add-on is the 0.5-1% of material I quality.Continue operation 3-5min, obtain material II;
Step 3, material II is joined in the stirrer, add the calcium lime powder of material II quality 5-10%, stir;
Step 4, in the stirrer operational process, slowly add clear water several times, control adds entry and the mixture mass ratio is to stop to add water behind the 40-50%;
Elder generation adds the aluminium powder of material II quality 1-2% in step 5, the stirrer, adds the calcium lime powder of material II quality 3-5% again, continues to stir; The aluminium powder trade mark is FLQ1, FLQ2 or FLQ3, granularity 0.08～0.10mm.
Step 6, in whipping process, will produce a large amount of ammonias, the negative pressure air-suction device cover through the stirrer top makes negative pressure value reach 60KPa, and the ammonia of collecting is derived;
Step 7, ammonia is imported in the multistage absorption device, wherein absorption liquid is that water reclaims ammonia and obtains the ammoniacal liquor 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, describedly in ball milling, add trolamine in the step 2 in the process as grinding aid based in a kind of method that from electrolytic manganese residues, directly extract to reclaim ammonia nitrogen, add-on is the 0.5-1% of material I quality.
Preferably, described based in a kind of method that from electrolytic manganese residues, directly extract to reclaim ammonia nitrogen, add calcium lime powder in step 3, the step 5; Produce Ca (OH) 2 through digestion; Manganese slag environment PH is elevated to more than 11, and, produces ammonia as whipping agent.
Preferably; Described based in a kind of method that from electrolytic manganese residues, directly extract to reclaim ammonia nitrogen; Calcium lime powder to using has following requirement: the calcium lime powder fineness requirement is not higher than 5% through the screen over-size of 120 mesh, and the content of free calcium oxide is not less than 85%.
Preferably, describedly add the aluminium powder of material II quality 1-2% in the step 5 based in a kind of method that from electrolytic manganese residues, directly extract to reclaim ammonia nitrogen, the aluminium powder trade mark is FLQ1, FLQ2 or FLQ3, granularity 0.08～0.10mm.
Preferably, described based in a kind of method that from electrolytic manganese residues, directly extract to reclaim ammonia nitrogen, the negative pressure air-suction device cover is installed in the stirrer top in the step 6, makes negative pressure value reach 60KPa, derives ammonia.
Preferably, describedly gas is imported in the multistage absorption device in the step 7 based in a kind of method that from electrolytic manganese residues, directly extract to reclaim ammonia nitrogen, absorption liquid reclaims ammonia during for water and obtains 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% dissolves.
Description of drawings
Fig. 1 directly extracts the process flow diagram that reclaims ammonia nitrogen for of the present invention being used for from electrolytic manganese waste residue.
Embodiment
Below in conjunction with accompanying drawing the present invention is done further detailed description, can implement according to this with reference to the specification sheets literal to make those skilled in the art:
Step 1, the electrolytic manganese residues that will just discharge obtain material I through fragmentation, dispersion, drying.
Step 2, the material I that obtains is carried out ball milling, add trolamine behind the operation 2-3min, continue operation 3-5min, obtain material II.
Step 3, material II is joined in the stirrer, add the calcium lime powder of material II quality 5-10%, stir; Calcium lime powder to using has following requirement: the calcium lime powder fineness requirement is not higher than 5% through the screen over-size of 120 mesh, and the content of free calcium oxide is not less than 85%.
Step 4, in the stirrer operational process, slowly add clear water several times, control adds entry and the mixture mass ratio is to stop to add water behind the 40-50%.
Elder generation adds the aluminium powder of material II quality 1-2% in step 5, the stirrer, adds the calcium lime powder of material II quality 3-5% again, continues to stir; The aluminium powder trade mark is FLQ1, FLQ2 or FLQ3, granularity 0.08～0.10mm.
Step 6, in whipping process, will produce a large amount of ammonias, the negative pressure air-suction device cover through the stirrer top makes negative pressure value reach 60KPa, and the ammonia of collecting is derived.
Step 7, ammonia is imported in the multistage absorption device, wherein absorption liquid is that water reclaims ammonia and obtains the ammoniacal liquor 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 (7)
1. one kind is directly extracted the method that reclaims ammonia nitrogen from electrolytic manganese residues, wherein, may further comprise the steps:
Step 1, the electrolytic manganese residues that will just discharge obtain material I through fragmentation, dispersion, drying;
Step 2, the material I that obtains is carried out ball milling, add trolamine behind the operation 2-3min, continue operation 3-5min, obtain material II;
Step 3, material II is joined in the stirrer, add the calcium lime powder of material II quality 5-10%, stir;
Step 4, in the stirrer operational process, slowly add clear water several times, control adds entry and the mixture mass ratio is to stop to add water behind the 40-50%;
Elder generation adds the aluminium powder of material II quality 1-2% in step 5, the stirrer, adds the calcium lime powder of material II quality 3-5% again, continues to stir;
Step 6, in whipping process, will produce ammonia,, the ammonia of collecting derived through the negative pressure air-suction device cover of stirrer top;
Step 7, ammonia is imported in the multistage absorption device, wherein absorption liquid is water or dilution heat of sulfuric acid, reclaims ammonia and obtains ammoniacal liquor and ammoniumsulphate soln.
2. like right 1 described technology, it is characterized in that: in ball milling, add trolamine in the step 2 in the process as grinding aid, add-on is the 0.5-1% of material I quality.
3. like right 1 described technology, it is characterized in that: add calcium lime powder in step 3, the step 5, produce Ca (OH) 2, manganese slag environment PH is elevated to more than 11, and, produce ammonia as whipping agent through digestion.
4. like right 3 described technologies, it is characterized in that: the calcium lime powder to using has following requirement: the calcium lime powder fineness requirement is not higher than 5% through the screen over-size of 120 mesh, and the content of free calcium oxide is not less than 85%.
5. like right 1 described technology, it is characterized in that: add the aluminium powder of material II quality 1-2% in the step 5, the aluminium powder trade mark is FLQ1, FLQ2 or FLQ3, granularity 0.08～0.10mm.
6. like right 1 described technology, it is characterized in that: the negative pressure air-suction device cover is installed in the stirrer top in the step 6, makes negative pressure value reach 60KPa, derives ammonia.
7. like right 1 described technology, it is characterized in that: in the step 7 gas is imported in the multistage absorption device, absorption liquid reclaims ammonia during for water and obtains the ammoniacal liquor that massfraction is 10-15%; Absorption liquid returns when being the dilution heat of sulfuric acid of 25-30% herds ammonia and obtains the ammoniumsulphate soln that massfraction is 5.5-7.5%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103570155A (en) * | 2013-10-16 | 2014-02-12 | 江苏晨力环保科技有限公司 | Manganese slag percolation wastewater treatment system and treatment method thereof |
| CN103817132A (en) * | 2013-12-13 | 2014-05-28 | 中国环境科学研究院 | Electrolytic manganese residue treatment system |
| CN104529196A (en) * | 2014-12-10 | 2015-04-22 | 北京科技大学 | Method for extracting ammonium and modifying electrolytic manganese residue |
| CN104891530A (en) * | 2015-05-18 | 2015-09-09 | 贵州省化工研究院 | Method for recycling ammonium groups from electrolytic manganese slag |
| CN106927507A (en) * | 2017-03-29 | 2017-07-07 | 湘潭市环境保护科学研究院 | One kind electrolysis MnO2The method for preparing manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer with waste residue containing Mn 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 |
| CN115382886A (en) * | 2022-08-10 | 2022-11-25 | 桂林理工大学 | Mechanical homogenization-low-temperature thermal activation accurate harmless treatment method for electrolytic manganese slag |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570155A (en) * | 2013-10-16 | 2014-02-12 | 江苏晨力环保科技有限公司 | Manganese slag percolation wastewater treatment system and treatment method thereof |
| 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 |
| CN103817132A (en) * | 2013-12-13 | 2014-05-28 | 中国环境科学研究院 | Electrolytic manganese residue treatment system |
| CN104529196A (en) * | 2014-12-10 | 2015-04-22 | 北京科技大学 | Method for extracting ammonium and modifying electrolytic manganese residue |
| CN104529196B (en) * | 2014-12-10 | 2017-01-11 | 北京科技大学 | Method for extracting ammonium and modifying electrolytic manganese residue |
| CN104891530A (en) * | 2015-05-18 | 2015-09-09 | 贵州省化工研究院 | Method for recycling ammonium groups from electrolytic manganese slag |
| CN106927507A (en) * | 2017-03-29 | 2017-07-07 | 湘潭市环境保护科学研究院 | One kind electrolysis MnO2The method for preparing manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer with waste residue containing Mn in electrolysis Mn productions |
| 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 |
| CN115382886A (en) * | 2022-08-10 | 2022-11-25 | 桂林理工大学 | Mechanical homogenization-low-temperature thermal activation accurate harmless treatment method for 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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