CN101597070B - Purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process in the sintering, palletizing and kiln processes and method thereof - Google Patents
Purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process in the sintering, palletizing and kiln processes and method thereof Download PDFInfo
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- CN101597070B CN101597070B CN2009100629690A CN200910062969A CN101597070B CN 101597070 B CN101597070 B CN 101597070B CN 2009100629690 A CN2009100629690 A CN 2009100629690A CN 200910062969 A CN200910062969 A CN 200910062969A CN 101597070 B CN101597070 B CN 101597070B
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Abstract
The invention relates to a purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process in the sintering, palletizing and kiln processes and a method thereof; the purifying device comprises a pH value adjusting box 1 and a centrifugal separating unit which are connected by a pipeline; a material transforming pump 4 is arranged on the connecting pipeline, an aerator 3 is connected at the lower part of the pH value adjusting box 1, and the centrifugal separating unit is a horizontal spiral discharging sedimentation centrifugal machine 2. The ammonia water in the flue gas desulfurization by ammonia process is utilized as a pH modifier of the ammonium sulphate solution and a metal ion remover, the ammonium sulphate solution is purified by aeration, chemical sedimentation and physical centrifugal separation, the purifying device has simple structure and is economic and practical, the quality of the separated ammonium sulphate solution can reach the requirements above the qualified products in national ammonium sulphate standard GB535-1995 after being concentrated, crystallized and dried.
Description
Technical field
The device and method that the flue gas that the present invention relates to produce in a kind of metallurgical industry sintering, pelletizing and the stove technology is purified with ammonia process of desulfurization afterproduct ammonium sulfate.
Background technology
Since the nineties in 20th century, China Steel industry is rapidly developed, and continuous 13 years crude steel output of China ranks first in the world.Rapid growth along with China's national economy, steel and iron industry will sustainable development in quite long one period, but owing in the smelting iron and steel production process, can consume a large amount of fuel and ore, produce a large amount of atmosphere pollutions, load to environment constantly increases the weight of, and this has become one of bottleneck of restriction sustainable development of iron and steel industry.At present, the SO of steel industry
2Account for about 11% of national every profession and trade discharge capacity etc. the Air Pollutant Emission amount, be only second to power industry, occupied the 2nd.The dust, the SO that produce of pelletizing, sintering process process wherein
2, CO
2Account for 40%～60% of steel industry annual emissions Deng discharge amount of pollution.Therefore, sintering, pelletizing and metallurgical furnace kiln flue gas are carried out SO
2Administer to the sustainable development of metallurgy industry and to improve the ecological environment and have great importance Deng pollutant emission.
The situation that current domestic sintering, pelletizing and stove smoke gas treatment present multiple technologies and deposits mainly contains ammonia-ammonia sulfate method, limestone-gypsum method, recirculating fluidized bed method, ionic liquid method etc.Wherein in the ammonia-process desulfurization technique technological process, the desulfurization afterproduct is an ammonium sulfate fertilizer, and its operating cost can be sold significantly by afterproduct and reduce, and is particularly suitable for the road of metallurgy industry recycling economy development.
The ammonia process technology of using both at home and abroad mainly contains following technology path at present:
(1) Walther ammonia process technology
Wet method ammoniacal liquor sulfur removal technology is to develop the technology in the ammonia process Walther of the seventies and eighties by Ke Lubai (krupp kroppers) company the earliest.Flue gas after the dedusting enters scrubbing tower earlier through over-heat-exchanger from the top, and with ammonia (25%) and stream and descend, ammoniacal liquor falls into the pond, circulated sprinkling flue gas in the usefulness pump suction absorption tower.Flue gas then enters a high-efficient washing tower behind demister, remaining salting liquid is washed out, after the cleaning flue gases after the heat exchanger heats enters chimney.
(2) AMASOX ammonia process technology
One of subject matter that traditional ammonia process technology runs into is to exist the aerosol problem not to be resolved in the flue gas after being purified.Can Jie Si-Bi Xiaofu company traditional ammonia process have been carried out transformation and improve be the AMASOX method.The main improvement is to change traditional multitower single tower of compact conformation into and settle the wet type electrostatic precipitator to solve the aerosol problem in tower.
(3) GE ammonia process technology
The nineties, the GE company of the U.S. has also developed ammonia process technology, this technological process is: the flue gas after the dedusting is drawn behind boiler of power plant, behind heat exchanger, enter the cooling of cooling device high-pressure spraying water smoke, dedusting (removing remaining flue dust), be cooled to enter into again in the absorption scrubbing tower near saturated and clean flue gas dew-point temperature.Be furnished with two sections in the absorption tower and absorb scrubber layer, make cleaning solution and flue gas be able to mixed fully the contact, after the wet electrical dust precipitator demist of the flue gas after the desulfurization in tower, enter heat exchanger again and heat up, reach discharge standard after chimney enters atmosphere.The cleaning solution that contains ammonium sulfate after the desulfurization forms afterproduct ammonium sulfate through crystal system.
(4) NKK ammonia process
The NKK ammonia process is the technology of NKK's exploitation.This absorption tower has certain characteristics, divides three sections.From the bottom up, hypomere is pre-wash dedusting and cold shock cooling, in this section, does not have the adding of absorbent.The stage casing is first absorber portion, and absorbent from then on section adds.Epimere does not still add absorbent as second absorber portion, only adds fresh water (FW).The flue gas heater via that absorbs after handling heats up back row to chimney.The ammonium sulfurous oxidation is carried out in independent oxidation reactor.The oxygen that needs is replenished by compressed air, and the oxidation residual gas is arranged to the absorption tower.
Above-mentioned multiple ammonia desulfurizing process is when metallurgy industry is used, owing to contain metal ingredient and dust such as more iron (mainly based on trivalent), copper, manganese, zinc, mercury, chromium, lead, aluminium in sintering, pelletizing and the stove flue gas, directly cause afterproduct ammonium sulfate quality lower.
Ammonia-process desulfurization technique is continued to use the power industry sulfur method more when removing mentioned component both at home and abroad at present, based on single one physical filter types such as filter or centrifuges, can not solve the ammonium sulfate quality problem at all.
Summary of the invention
The objective of the invention is in order to overcome existing sintering, pelletizing, the low problem of stove flue gas employing ammonia process of desulfurization afterproduct ammonium sulfate quality, a kind of purifying device of ammonium sulphate solution and method are provided, impurity such as metal in the ammonium sulfate and dust are separated, made metallurgy industry sintering and pelletizing produced by flue gas desulfurization by ammonia process ammonium sulfate quality reach the above requirement of certified products in the national ammonium sulfate standard " GB535-1995 ".
The object of the invention realizes by following technical solution:
Dust complicated component in sintering, pelletizing and the stove flue gas, in the ammonia desulfurizing process process, in the afterproduct ammonium sulfate, bring metal ingredients such as more dust and iron, copper, manganese, zinc, mercury, chromium, lead, aluminium inevitably into, influence the quality of ammonium sulfate crystallization.(NH in the ammonia process of desulfurization tower
4)
2SO
3-(NH
4)
2SO
4Circulation fluid is after the aeration oxidation, and pH value is generally about 2～5.5 according to the process route difference in the tower.Metal ingredients such as iron, copper, manganese, zinc, mercury, arsenic, lead, aluminium generally exist with the dissolving salt form, and the solution metal composition generally has: Fe
2+, Fe
3+, Cu
2+, Mn
2+, Zn
2+, Hg
2+, Cr
3+, Pb
2+, Al
3+, Ca
2+, Na
+, K
+Deng.
For removing metal ion and the dust in sintering, pelletizing and the stove ammonium sulphate solution produced by flue gas desulfurization by ammonia process, purifying plant provided by the invention, comprise and transfer pH value case, centrifugal separation unit, transfer the pH value case to be connected by pipeline with centrifugal separation unit, transfering material pump is set on connecting pipe, connect aerator in the bottom of transferring the pH value case, centrifugal separation unit is a horizontal spiral discharge sedimentation centrifuge.
Adopt purifying plant of the present invention, the method to sintering, pelletizing and stove ammonium sulphate solution produced by flue gas desulfurization by ammonia process are purified comprises the steps:
1. the ammonium sulfate that generates in sweetening process of ammonia process of desulfurization tower enters by pipeline and transfers the pH value case, is transferring pH value case bottom to blast air by aerator, and the purpose of aeration is to utilize airborne oxygen with the Fe in the ammonium sulfate
2+Be oxidized to Fe
3+, form Fe (OH)
3Precipitation.Has the effect of stirring average simultaneously.The chemical reaction that takes place is:
Fe
2++O
2+H
2O→Fe(OH)
3↓
2. in aeration, in transferring the pH value case, add the ammoniacal liquor that the ammonia process of desulfurization is used, will transfer the interior ammonium sulfate pH value of pH value case to be adjusted into 7～8 by pipeline.At this moment, in solution, will take place below the reaction:
Fe
3++3OH
-＝Fe(OH)
3↓
Cu
2++2OH
-＝Cu(OH)
2↓
Zn
2++2OH
-＝Zn(OH)
2↓
Pb
2++2OH
-＝Pb(OH)
2↓
Al
3++3OH
-＝Al(OH)
3↓
Cr
3++3OH
-＝Cr(OH)
3↓
3. by after transferring pH value and stirring, most metal all can form precipitation of hydroxide and separate out.And then by transferring pH value case transfering material pump and pipeline will transfer the ammonium sulfate of pH value to be driven in the horizontal spiral discharge sedimentation centrifuge.
4. by the effect of horizontal spiral discharge sedimentation centrifuge, the precipitate metal hydroxides and the dust of the different-grain diameter in the ammonium sulfate can be isolated, the ammonium sulfate quality can be improved.
5. the ammonium sulfate of isolating precipitate metal hydroxides and dust enters the finished product case, pH value is an alkalescence in the ammonium sulfate finished product case at this moment, can transfer pH value again by the condensate liquid that adds in dilute sulfuric acid or the follow-up ammonium sulfate concentration and crystallization process, the pH value requirement is driven in the follow-up condensing crystallizing drying process by ammonium sulfate finished product case pump and pipeline then when making it to meet follow-up ammonium sulfate condensing crystallizing.
Horizontal spiral discharge sedimentation centrifuge can efflux waste residue in deimpurity process, main component is the precipitated metal thing in these waste residues, and after can collecting by gathering-device, special project is disposed or turned back to utilization again in sintering or the pelletizing process according to its composition.
The invention has the beneficial effects as follows: the present invention utilizes ammoniacal liquor in the ammonia desulfurizing process as the PH conditioning agent and the metal ion remover of ammonium sulfate, adopt the method for aeration, chemical neutralization precipitation and physics centrifugation that sintering, pelletizing and stove ammonium sulphate solution produced by flue gas desulfurization by ammonia process are purified, purifying plant is simple in structure, economic and practical, can efficiently remove various metal ingredients and dust in the metallurgy industry sintering machine pelletizing ammonium sulphate solution produced by flue gas desulfurization by ammonia process.Ammonium sulfate after the separation is by after the condensing crystallizing drying, and quality can reach the above requirement of certified products in the national ammonium sulfate standard " GB535-1995 ".
Description of drawings
Fig. 1 one-level of the present invention is separated purifying plant figure
Fig. 2 secondary of the present invention separates purifying plant figure
1. transfer pH value case, 2. horizontal spiral discharge sedimentation centrifuge, 3. aerator, 4. transfering material pump, 5. finished product case, 6. agitator, 7. removing heavy metals case, 8. horizontal spiral discharge sedimentation centrifuge, 9. transfering material pump among the figure.
The specific embodiment
The present invention is described further below in conjunction with accompanying drawing:
Sintering, pelletizing or stove smoke components change along with the variation of raw material, in actual engineering, when heavy metal concentration in the flue gas is low, adopting as shown in Figure 1 one-level to separate purifying plant can make in the ammonium sulfate metal ingredient and dust remove up to standard, this one-level purifying plant comprises transfers pH value case 1, horizontal spiral discharge sedimentation centrifuge 2, transfer pH value case 1 and horizontal spiral discharge sedimentation centrifuge 2 to be connected by pipeline, transfering material pump 4 is set on connecting pipe, connect aerator 3 in the bottom of transferring pH value case 1, the outlet of horizontal spiral discharge sedimentation centrifuge 2 is connected with finished product case 5 by pipeline, establishes agitator in transferring pH value case 1 and finished product case 5.
Adopt the method for purification of one-level purifying plant as follows:
1. aerator 3 is to transferring pH value case 1 to blast air;
2. in transferring pH value case 1, add the used ammoniacal liquor of the ammonia process of desulfurization, will transfer pH value case 1 interior ammonium sulfate pH value to be adjusted into 7～8;
3. transfering material pump 4 will transfer in the pH value case 1 ammonium sulfate to squeeze into horizontal spiral discharge sedimentation centrifuge 2;
4. horizontal spiral discharge sedimentation centrifuge 2 is isolated precipitate metal hydroxides and the dust in the ammonium sulfate;
5. the ammonium sulfate of isolating precipitate metal hydroxides and dust enters finished product case 5.
When the heavy metal constituent concentration is higher in the flue gas, because the adjustable range of pH value is between 7～8, after isolating most metal ion, in solution, still has some metal ions and can't be completed into precipitation of hydroxide and removed, mainly contain Mn
2+, Zn
2+, Cu
2+, Pb
2+Deng, adopt secondary as shown in Figure 2 to separate purifying plant, can further remove heavy metal ion.Secondary separates purifying plant and comprises accent pH value case 1, one-level horizontal spiral discharge sedimentation centrifuge 2, removing heavy metals case 7, secondary horizontal spiral discharge sedimentation centrifuge 8.Transfer pH value case 1 and one-level horizontal spiral discharge sedimentation centrifuge 2 to be connected by pipeline, transfering material pump 4 is set on connecting pipe, connect aerator 3 in the bottom of transferring pH value case 1, the outlet of one-level horizontal spiral discharge sedimentation centrifuge 2 is connected with removing heavy metals case 7 by pipeline, 7 outlets of removing heavy metals case are connected with secondary horizontal spiral discharge sedimentation centrifuge 8 by the transfering material pump 9 that is provided with on pipeline and the pipeline, the outlet of secondary horizontal spiral discharge sedimentation centrifuge 8 is connected with finished product case 5 by pipeline and pump, establishes agitator in transferring pH value case 1, removing heavy metals 7, finished product case 5.
Adopt the method for purification of secondary purifying plant as follows:
1. aerator 3 is to transferring pH value case 1 to blast air;
2. in transferring pH value case 1, add the used ammoniacal liquor of the ammonia process of desulfurization, will transfer pH value case 1 interior ammonium sulfate pH value to be adjusted into 7～8;
3. transfering material pump 4 will transfer in the pH value case 1 ammonium sulfate to squeeze into horizontal spiral discharge sedimentation centrifuge 2;
4. horizontal spiral discharge sedimentation centrifuge 2 is isolated precipitate metal hydroxides and the dust in the ammonium sulfate;
5. the ammonium sulfate of isolating precipitate metal hydroxides and dust enters removing heavy metals case 7, adds the sulfide heavy metal remover in removing heavy metals case 7, makes heavy metal form the metal sulphide precipitation and separates out;
The main reaction that takes place is:
Mn
2++S
2-＝MnS↓
Cu
2++S
2-＝CuS↓
Zn
2++S
2-＝ZnS↓
Pb
2++S
2-＝PbS↓
6. the ammonium sulfate that has removed heavy metal is squeezed into horizontal spiral discharge sedimentation centrifuge (8) by transfering material pump (9), and the ammonium sulfate of isolating heavy metal precipitation through horizontal spiral discharge sedimentation centrifuge (8) enters finished product case (5).
In the ammonia type flue gas desulfurizing process, ammonium sulfate condensing crystallizing process is intermitten service.In practical engineering application, can implement according to the secondary purifying plant, the secondary purifying plant is divided into the two-stage centrifugal separative element, transfer pH value case 1, transfering material pump 4 and horizontal spiral discharge sedimentation centrifuge 2 to form the first-stage centrifugal separative element, removing heavy metals case 7, transfering material pump 9, horizontal spiral discharge sedimentation centrifuge 8 are formed the secondary centrifugal separation unit.When ammonium sulfate concentrations does not reach condensing crystallizing in the desulfurizing tower, the secondary centrifugal separation unit is out of service, slurries after the removal of impurity of first-stage centrifugal separative element directly enter into ammonium sulfate finished product case 5, be driven in the desulfurizing tower by ammonium sulfate finished product case pump and pipeline again, carry out the circulation removal of impurity process of system.When ammonium sulfate concentrations in the desulfurizing tower reaches the condensing crystallizing condition, open the secondary centrifugal separation unit, with the ammonium sulfate in the ammonium sulfate finished product case 5, be driven in the follow-up condensing crystallizing drying system simultaneously, carry out the production of ammonium sulfate by ammonium sulfate finished product case pump and pipeline.
Claims (6)
1. a sintering, pelletizing and stove purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process, comprise adjust pH case (1), centrifugal separation unit, adjust pH case (1) is connected by pipeline with centrifugal separation unit, transfering material pump (4) is set on connecting pipe, bottom at adjust pH case (1) connects aerator (3), and centrifugal separation unit is horizontal spiral discharge sedimentation centrifuge (2).
2. a kind of sintering as claimed in claim 1, pelletizing and stove purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process, it is characterized in that connecting removing heavy metals case (7) in the outlet of horizontal spiral discharge sedimentation centrifuge (2), removing heavy metals case (7) outlet is connected with another horizontal spiral discharge sedimentation centrifuge (8) by the transfering material pump (9) that is provided with on pipeline and the pipeline.
3. a kind of sintering as claimed in claim 1 or 2, pelletizing and stove purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process is characterized in that (7) are provided with agitator (6) in adjust pH case (1) and removing heavy metals case.
4. a sintering, pelletizing and stove ammonium sulphate solution produced by flue gas desulfurization by ammonia process method of purification comprise following characterization step:
1. aerator (3) blasts air to adjust pH case (1);
2. in adjust pH case (1), add the used ammoniacal liquor of the ammonia process of desulfurization, the interior ammonium sulfate pH of adjust pH case (1) value is adjusted into 7～8;
3. transfering material pump (4) is squeezed into horizontal spiral discharge sedimentation centrifuge (2) with ammonium sulfate in the adjust pH case (1);
4. horizontal spiral discharge sedimentation centrifuge (2) is isolated precipitate metal hydroxides and the dust in the ammonium sulfate;
5. the ammonium sulfate of isolating precipitate metal hydroxides and dust enters finished product case (5).
5. a kind of sintering as claimed in claim 4, pelletizing and stove ammonium sulphate solution produced by flue gas desulfurization by ammonia process method of purification, it is characterized in that the isolated ammonium sulfate of horizontal spiral discharge sedimentation centrifuge (2) enters removing heavy metals case (7), in removing heavy metals case (7), add the heavy metal remover, the ammonium sulfate that has removed heavy metal is squeezed into horizontal spiral discharge sedimentation centrifuge (8) by transfering material pump (9), and the ammonium sulfate of isolating heavy metal through horizontal spiral discharge sedimentation centrifuge (8) enters finished product case (5).
6. a kind of sintering as claimed in claim 5, pelletizing and stove ammonium sulphate solution produced by flue gas desulfurization by ammonia process method of purification is characterized in that the heavy metal remover is a sulfide.
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|---|---|---|---|
| CN2009100629690A CN101597070B (en) | 2009-07-03 | 2009-07-03 | Purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process in the sintering, palletizing and kiln processes and method thereof |
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|---|---|---|---|
| CN2009100629690A CN101597070B (en) | 2009-07-03 | 2009-07-03 | Purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process in the sintering, palletizing and kiln processes and method thereof |
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| CN101597070B true CN101597070B (en) | 2011-04-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350202A (en) * | 2011-08-11 | 2012-02-15 | 武汉都市环保工程技术股份有限公司 | System for desulfuration and ash removal of flue gas from steel plant sintering by ammonia method |
| CN102515200A (en) * | 2011-11-25 | 2012-06-27 | 武汉兴能环保技术有限公司 | Method for removing heavy metals in by-product of ammonia desulphurization |
| CN103638695B (en) * | 2013-12-27 | 2016-03-30 | 云南铝业股份有限公司 | The minimizing technology of metal impurities in a kind of calcining petroleum coke flue gas ammonia method desulfurizing technique |
| CN103708502B (en) * | 2014-01-03 | 2015-12-30 | 武汉科技大学 | A kind of method of desulfuration byproduct ammonium sulfate purifying |
| CN104003421A (en) * | 2014-05-29 | 2014-08-27 | 伊犁川宁生物技术有限公司 | Method for removing impurities in desulfurization and denitrification by-products |
| CN106268251A (en) * | 2016-08-08 | 2017-01-04 | 贵州赤天化桐梓化工有限公司 | A kind of ammonia process of desulfurization enriching section solution PH adjusting means |
| CN107321154B (en) * | 2017-05-16 | 2020-08-25 | 上海交通大学 | Ammonia flue gas desulfurization system and method |
| CN109399667A (en) * | 2018-12-14 | 2019-03-01 | 湖南江冶机电科技股份有限公司 | A kind of method and equipment of lead plaster ammonium method desulfurizing byproduct-ammonium sulfate deep purifying |
| CN110921958A (en) * | 2019-12-17 | 2020-03-27 | 武汉钢铁有限公司 | Acid-making wastewater recycling system and method by sintering flue gas activated carbon desulfurization process |
| CN116639708A (en) * | 2023-06-13 | 2023-08-25 | 山东大成生物化工有限公司 | Method and device for recycling ammonium sulfate from fosetyl-aluminum production waste liquid |
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