CN102423613B - Ammonia desulfurization method for effectively removing chlorine and fluorine ions and heavy metal ions - Google Patents
Ammonia desulfurization method for effectively removing chlorine and fluorine ions and heavy metal ions Download PDFInfo
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- CN102423613B CN102423613B CN 201110242899 CN201110242899A CN102423613B CN 102423613 B CN102423613 B CN 102423613B CN 201110242899 CN201110242899 CN 201110242899 CN 201110242899 A CN201110242899 A CN 201110242899A CN 102423613 B CN102423613 B CN 102423613B
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- tower
- flue gas
- prewashing
- desulfurizing
- ammonium
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 25
- 239000000460 chlorine Substances 0.000 title claims abstract description 23
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 21
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 15
- 230000023556 desulfurization Effects 0.000 title claims abstract description 13
- 150000002500 ions Chemical class 0.000 title claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 title abstract 2
- 239000011737 fluorine Substances 0.000 title abstract 2
- -1 fluorine ions Chemical class 0.000 title abstract 2
- 239000003546 flue gas Substances 0.000 claims abstract description 67
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000000428 dust Substances 0.000 claims abstract description 24
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 22
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 6
- 231100000719 pollutant Toxicity 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 230000003009 desulfurizing effect Effects 0.000 claims description 92
- 230000003647 oxidation Effects 0.000 claims description 42
- 238000007254 oxidation reaction Methods 0.000 claims description 42
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 41
- 238000010521 absorption reaction Methods 0.000 claims description 30
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 21
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005273 aeration Methods 0.000 claims description 14
- 239000013505 freshwater Substances 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- 239000003905 agrochemical Substances 0.000 claims description 3
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000006276 transfer reaction Methods 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims description 2
- 239000003337 fertilizer Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000008235 industrial water Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 9
- 238000013459 approach Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000035800 maturation Effects 0.000 description 5
- 241000370738 Chlorion Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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- Treating Waste Gases (AREA)
Abstract
The invention relates to an ammonia desulfurization method for effectively removing chlorine and fluorine ions and heavy metal ions. The invention is characterized in that prewashing is carried out before flue gas enters into a desulfurization tower, industrial water and/or circulating water can be used as washing liquid in a prewashing tower, circular spraying and washing are performed, 90-95% Cl<-> and F<-> in flue gas are removed, 70%-80% soluble metal ions Fe<3+>, Hg<2+> and Pb<2+> can be removed, 70%-80% of dust is removed, the washed pollutant is sent to a waste water treatment system through slurry-containing waste water discharged from the bottom of the tower for treating to reach the standard and then discharge. The ammonia desulfurization method of the invention can thoroughly eliminate the problems that severe equipment corrosion is caused by enrichment of Cl<-> and F<-> on the desulphurization system, and heavy metal of the finished product fertilizer exceeds the standard.The desulphurization byproduct ammonium sulfate fertilizer obtained by the method can reach or exceed the quality standard of the national standard superior products.
Description
Technical field
The present invention relates to a kind of new ammonia desulfuration equipment and method, particularly a kind of ammonia (ammoniacal liquor, liquefied ammonia) that utilizes that can effectively remove chlorine, fluorine ion and reduction byproduct heavy metal ion content removes the method for sulfur dioxide in flue gas as absorbent.
Background technology
At present, ammonia process removes the mode that sulfur dioxide in flue gas mainly adopts spray to absorb, and absorption technique mainly is divided into single tower absorption and double tower absorbs two kinds.
The ammonia process of desulfurization absorption technique of external exploitation is to adopt the double tower form the earliest, and at present domestic also also have similar desulfurizer to use.Traditional double tower absorption plant is that condensing crystallizing tower and absorption tower are composed in series, and flue gas at first enters the condensing crystallizing tower, and cooling, cleaning dust utilize the heat in the flue gas that absorption liquid is carried out condensing crystallizing simultaneously in the condensing crystallizing tower.Flue gas enters the absorption tower after leaving the condensing crystallizing tower, finishes the absorbing and removing of sulfur dioxide in the absorption tower.
Afterwards, external, domesticly all ammonia process of desulfurization absorption technique was improved, and wherein just had to change the double tower absorption technique into single tower absorption technique.At present the single tower absorption plant that adopts mainly contains two kinds of hollow-spraying-tower and packed towers, and single tower absorption plant is simple in structure, absorbs, concentrates, crystallization all finishes in a tower.
At present, no matter be traditional double tower absorption technique or improve after single tower absorption technique, all have an insoluble problem, that is exactly that chlorion, fluorine ion and heavy metal ion in the flue gas can constantly enrichment in desulfurization slurry.On the one hand device is produced serious corrosion, cause the ammonium sulfate fertilizer quality of by-product to descend on the other hand, the serious content of beary metal that also can cause exceeds standard, and brings heavy metal pollution of soil.
Summary of the invention
The objective of the invention is provides a kind of new ammonia method desulfurizing method that effectively removes chlorine, fluorine ion and heavy metal ion in order to overcome the deficiency that above-mentioned prior art exists.Chlorion in the effectively removal system of the present invention and fluorine ion, and reduce heavy metal ion content in the producing ammonium sulfate byproduct chemical fertilizer significantly, satisfy national agrochemical standard-required.
Technical scheme of the present invention is:
Effectively remove chlorine, the ammonia desulfuration equipment of fluorine ion and heavy metal ion, comprise the prewashing tower, prewashing tower circulating pump, the fresh water shower, prewashing tower circulated sprinkling pipe, prewashing tower mud excavationg pump, prewashing tower flue demister, desulfurizing tower, the desulfurizing tower circulating pump, desulfurizing tower circulated sprinkling pipe, the desulfurizing tower demister, the desulfurizing tower excavationg pump, oxidation tank, the oxidation tank blast pipe, oxidation fan, aeration tube, the ammonium sulfate excavationg pump, aqua ammonia pump, it is characterized in that: be provided with smoke inlet at the prewashing top of tower, be provided with the mud outlet at the prewashing tower bottom, be provided with the recirculated water outlet in prewashing tower bottom, be provided with exhanst gas outlet at prewashing tower middle part, be separately installed with the fresh water shower on prewashing tower top, prewashing tower circulated sprinkling pipe, prewashing tower circulating pump is connected between recirculated water outlet and the prewashing tower circulated sprinkling pipe, prewashing tower mud excavationg pump links to each other with the mud outlet, fresh water shower external water pipe, prewashing tower flue demister is installed in prewashing tower flue gas exit; The middle part of desulfurizing tower is provided with gas approach, the top of desulfurizing tower is provided with exhanst gas outlet, desulfurizing tower circulated sprinkling pipe is installed above the gas approach of desulfurizing tower, the desulfurizing tower demister is installed above the desulfurizing tower circulated sprinkling pipe of desulfurizing tower, be respectively equipped with the slurries circulation port in the bottom of desulfurizing tower, slurries outlet and ammoniacal liquor inlet, aqua ammonia pump links to each other with the ammoniacal liquor inlet, the desulfurizing tower circulating pump is connected between slurries circulation port and the desulfurizing tower circulated sprinkling pipe, the desulfurizing tower excavationg pump is connected between slurries outlet and the oxidation tank, the oxidation tank bottom is provided with the ammonium sulfate outlet and links to each other with the ammonium sulfate excavationg pump, the oxidation tank top is provided with gas vent, aeration tube is installed in the oxidation tank, and aeration tube links to each other with oxidation fan.
This device is provided with the gas access and links to each other with the gas vent of oxidation tank by pipe at desulfurizing tower.
Effectively remove the ammonia method desulfurizing method of chlorine, fluorine ion and heavy metal ion, it is characterized in that carrying out according to the following steps:
(1), the flue gas that contains sulfur dioxide at first enters the prewashing tower from prewashing tower bottom smoke inlet, the prewashing tower adopts void tower, column plate tower or tubulent contact tower, the prewashing tower uses industry water and/or recirculated water to make cleaning solution, in tower by prewashing tower circulating pump circulated sprinkling;
(2), flue gas fully contacts the Cl in the flue gas with cleaning solution
-, F
-90-95% is removed, and the metal ion of solubility is such as Fe
3+, Hg
2+, Pb
2+70%-80% is removed, and dust 70%-80% is removed; Along with cleaning solution circulation cleaning in the prewashing tower, the cleaning solution pH value descends gradually, contain mud waste water and additional fresh water by discharging from the tower bed mud slurry outlet of prewashing tower, the cleaning solution pH value is between 2.2-2.8 in the control prewashing tower, pH value is positioned at this interval cleaning solution and only absorbs HCl, HF, soluble metal ion and dust, to SO
2There is not absorption;
(3), wash away most Cl
-, F
-With most of Fe
3+, Hg
2+, Pb
2+The flue gas of soluble metal ion and dust leaves the prewashing tower, enters desulfurizing tower after removing droplets entrained by demister;
(4), the mud waste water that contains of discharging at the bottom of the prewashing Tata delivers to Waste Water Treatment and handles qualified discharge, Waste Water Treatment be technology and the device of present general maturation;
(5), after flue gas enters desulfurizing tower, in desulfurizing tower, flue gas upwards absorbs processing by spraying layer, flue gas is by spraying layer, carries out counter current contacting with the absorption liquid of spray, mass transfer and absorption reaction takes place, to remove the SO in the flue gas
2, SO
3And a small amount of remaining HCl, HF and dust; After flue gas passed spraying layer, the pollutant in the flue gas substantially all removed, and after clean flue gas is removed droplets entrained by demister, discharged outside the tower;
(6), ammoniacal liquor is sent in the desulfurizing tower ammoniacal liquor or the preparation of use liquefied ammonia that ammoniacal liquor can use industrial deposed ammonia, market to buy by aqua ammonia pump; Ammoniacal liquor adds in the desulfurization Tata prime cement pond, fully mixes with slurries in the tower; Slurries in the tower mainly are ammonium sulfite solutions, and ammonium sulfite solution is main desulfurization absorbent; Ammonium sulfite solution is by the desulfurizing tower circulating pump, and circulated sprinkling absorbs the SO in the flue gas
2, generate ammonium bisulfite, when the bisulfite ammonium concentration in the slurries was higher, desulfuration efficiency can descend gradually until losing desulphurizing ability fully; By add ammoniacal liquor in the slurries pond, ammoniacal liquor and ammonium bisulfite reaction generate ammonium sulfite, remain between the 5.2-5.8 by the pH value that adds ammoniacal liquor adjusting slurries, make slurries keep enough desulphurizing abilities; Here, the effect of ammoniacal liquor reality is desulfurizing agent regeneration, and real desulfurizing agent is ammonium sulfite solution, has so also avoided ammonia and the SO in the gas phase effectively
2, SO
3Reaction generates aerosol;
When (7), solution quality concentration reaches 35%-40% in the desulfurizing tower stock tank, by the desulfurizing tower excavationg pump ammonium sulfite solution is got to oxidation tank, be furnished with aeration tube in the oxidation tank, oxidation fan blasts air by aeration tube to the ammonium sulfite solution in the oxidation tank, and making sulfite oxidation is ammonium sulfate;
(8), after the ammonium sulfate of fully oxidation delivers to ammonium sulfate byproduct for treatment system and carry out evaporative crystallization, drying, packing by sulphur ammonium excavationg pump, become qualified agrochemical.Ammonium sulfate byproduct for treatment system adopts general mature technology and device at present.
The present invention has following good effect:
Remove most Cl in the flue gas by prewashing
-, F
-With most of Fe
3+, Hg
2+, Pb
2+Soluble metal ion and dust, the pollutant of deviating from is handled qualified back qualified discharge by Waste Water Treatment.Thoroughly eliminated desulphurization system because Cl
-, F
-The phenomenon of the serious and finished product chemical fertilizer heavy metals exceeding standard of the equipment corrosion that enrichment causes.And because the prewashing tower also has dedusting and cool effect, be particularly suitable for the higher flue gas of dust content and handle, and the flue gas after the cooling has at utmost suppressed the generation of aerosol secondary pollution.
According to the lab scale test, adopt technology of the present invention, the desulfuration byproduct content of beary metal declines to a great extent, and sees the following form:
In addition, adopt traditional ammonia desulfurizing process, because can not efflux wastewater, the chlorion of enrichment, fluorine ion can only be discharged by final products in the system, must be accumulated to very high concentration like this and just can reach balance.Show that chlorine ion concentration reaches more than the 60000ppm in the final system through domestic a plurality of actual items, fluorinion concentration has also reaches 8000ppm, and equipment and pipeline corrosion is serious.Adopt technology of the present invention, the chlorion equilibrium concentration is less than 6000ppm in the desulfurizing tower, and fluorinion concentration is less than 500ppm.
Description of drawings
Fig. 1 is process chart of the present invention.
The specific embodiment
As shown in Figure 1, the used device of the present invention comprises prewashing tower 6, prewashing tower circulating pump 4, fresh water shower 2, prewashing tower circulated sprinkling pipe 3, prewashing tower mud excavationg pump 5, prewashing tower flue demister 8, desulfurizing tower 10, desulfurizing tower circulating pump 11, desulfurizing tower circulated sprinkling pipe 12, desulfurizing tower demister 13, desulfurizing tower excavationg pump 15, oxidation tank 16, oxidation tank blast pipe 17, oxidation fan 18, aeration tube 19, ammonium sulfate excavationg pump 20, aqua ammonia pump 21, be provided with smoke inlet 1 at the prewashing top of tower, be provided with the mud outlet at the prewashing tower bottom, be provided with the recirculated water outlet in prewashing tower bottom, be provided with exhanst gas outlet 7 at prewashing tower middle part, be separately installed with fresh water shower 2 on prewashing tower top, prewashing tower circulated sprinkling pipe 3, prewashing tower circulating pump 4 is connected between recirculated water outlet and the prewashing tower circulated sprinkling pipe 3, prewashing tower mud excavationg pump 5 links to each other with the mud outlet, fresh water shower 2 external water pipes, prewashing tower flue demister 8 is installed in the prewashing tower flue gas and exports 7 places; The middle part of desulfurizing tower 10 is provided with gas approach 9, the top of desulfurizing tower is provided with exhanst gas outlet 14, desulfurizing tower circulated sprinkling pipe 12 is installed above the gas approach 9 of desulfurizing tower, desulfurizing tower demister 13 is installed above the desulfurizing tower circulated sprinkling pipe 12 of desulfurizing tower, be respectively equipped with the slurries circulation port in the bottom of desulfurizing tower, slurries outlet and ammoniacal liquor inlet, aqua ammonia pump 21 links to each other with the ammoniacal liquor inlet, desulfurizing tower circulating pump 11 is connected between slurries circulation port and the desulfurizing tower circulated sprinkling pipe 12, desulfurizing tower excavationg pump 15 is connected between slurries outlet and the oxidation tank 16, oxidation tank 16 bottoms are provided with the ammonium sulfate outlet and link to each other with ammonium sulfate excavationg pump 20, oxidation tank 16 tops are provided with gas vent 17, aeration tube 19 is installed in the oxidation tank 16, and aeration tube 19 links to each other with oxidation fan 18.This device is provided with the gas access and links to each other with the gas vent 17 of oxidation tank 16 by pipe at desulfurizing tower 10.
As shown in Figure 1,120 ℃ of-160 ℃ of former flue gases enter prewashing tower 6 by prewashing tower flue gas entrance 1, at first spray into fresh water by fresh water shower 2, make flue-gas temperature drop to 80 ℃-100 ℃, flue gas fully contacts with the cleaning solution of prewashing tower circulated sprinkling pipe 3 sprays in prewashing tower 6, flue-gas temperature drops to 50-60 ℃, the Cl in the flue gas
-, F
-90%-95% is removed, and the metal ion of solubility is such as Fe
3+, Hg
2+, Pb
2+70%-80% is removed, and dust 70%-80% is removed; Wash away most Cl
-, F
-With most of Fe
3+, Hg
2+, Pb
2+The flue gas of soluble metal ion and dust leaves prewashing tower 6 from prewashing tower flue gas outlet 7, enters desulfurizing tower 10 from desulfurizing tower gas approach 9 after removing droplets entrained by prewashing tower flue demister 8;
Prewashing tower 6 interior cleaning solutions are got to prewashing tower circulated sprinkling pipe 3 by prewashing tower circulating pump 4 and are carried out the circulated sprinkling washing, the dust that washs in the cleaning solution precipitates at the bottom of tower, the cleaning solution that will contain mud by prewashing tower mud excavationg pump 5 is delivered to Waste Water Treatment and is handled, qualified discharge, Waste Water Treatment adopts technology and the device of at present general maturation.Efflux and replenish fresh water by mud, the absorption liquid pH value is between 2.2-2.8 in the control prewashing tower.
Flue gas enters desulfurizing tower 10 backs and rises in desulfurizing tower 10, with the absorption liquid counter current contacting of desulfurizing tower circulated sprinkling pipe 12 sprays, mass transfer takes place absorb the SO in the flue gas
2, SO
3And pollutants such as a small amount of remaining HCl, HF and dust are absorbed washing, meet the requirements of to continue behind the desulfuration efficiency upwards, to discharge from desulfurizing tower exhanst gas outlet 14 except the droplet of deentrainment by desulfurizing tower demister 13.
The desulfurizing tower absorption liquid is extracted out from desulfurizing tower 10 bottoms by desulfurizing tower circulating pump 11 and is got to desulfurizing tower shower 12, and absorption liquid is constantly absorbing SO in the flue gas
2, SO
3, absorption liquid Central Asia ammonium sulfate concentrations can be more and more higher, when ammonium sulfite concentration reaches 35%-40%, gets to oxidation tank 16 near saturated back with desulfurizing tower excavationg pump 15.
The ammoniacal liquor that the ammonia process of desulfurization is used is sent in the desulfurizing tower 10 by aqua ammonia pump 21, ammoniacal liquor or the preparation of use liquefied ammonia that ammoniacal liquor can use industrial deposed ammonia, market to buy.Ammoniacal liquor adds in the desulfurizing tower 10 tower prime cement ponds, fully mixes with slurries in the tower.Slurries in the tower mainly are ammonium sulfite solutions, and ammonium sulfite solution is main desulfurization absorbent.Ammonium sulfite solution is got to desulfurizing tower circulated sprinkling pipe 12 by desulfurizing tower circulating pump 11, and circulated sprinkling absorbs the SO in the flue gas
2, generate ammonium bisulfite, when the bisulfite ammonium concentration in the slurries was higher, desulfuration efficiency can descend gradually until losing desulphurizing ability fully.By add ammoniacal liquor in the slurries pond, ammoniacal liquor and ammonium bisulfite reaction generate ammonium sulfite, remain between the 5.2-5.8 by the pH value that adds ammoniacal liquor adjusting slurries, make slurries keep enough desulphurizing abilities.Here, the effect of ammoniacal liquor reality is desulfurizing agent regeneration, and real desulfurizing agent is ammonium sulfite solution
Embodiment 1
As shown in Figure 1, be 130 ℃ flue gas from the temperature of boiler, flow is 1.2 * 10
6Standard cubic meter/hour, sulfur dioxide in flue gas concentration is 3000mg/Nm
3, dust content is 100mg/Nm
3This flue gas enters prewashing tower 6 from prewashing tower flue gas entrance 1, sprays into fresh water spraying cooling to 80 ℃ by fresh water shower 2, and flue gas fully contacts with the cleaning solution of prewashing tower circulated sprinkling pipe 3 sprays in prewashing tower 6, and flue-gas temperature drops to 56 ℃, the Cl in the flue gas
-, F
-95% be removed, and the metal ion of solubility is such as Fe
3+, Hg
2+, Pb
2+70%-80% is removed, and dust 70%-80% is removed, and washes away most Cl
-, F
-With most of Fe
3+, Hg
2+, Pb
2+The flue gas of soluble metal ion and dust leaves prewashing tower 6 from prewashing tower flue gas outlet 7, enters desulfurizing tower 10 from desulfurizing tower gas approach 9 after removing droplets entrained by prewashing tower flue demister 8;
The dust that washs in prewashing tower 6 cleaning solutions precipitates at the bottom of tower, and the cleaning solution that will contain mud by prewashing tower mud excavationg pump 5 is delivered to Waste Water Treatment and handled, qualified discharge, and Waste Water Treatment adopts technology and the device of at present general maturation.Efflux and replenish fresh water by mud, the absorption liquid pH value is between 2.2-2.8 in the control prewashing tower.Like this, the most Cl in the flue gas
-, F
-With most of Fe
3+, Hg
2+, Pb
2+Soluble metal ion and dust are discharged system by wastewater treatment;
Flue gas enters desulfurizing tower 10 backs and rises in desulfurizing tower 10, with the absorption liquid counter current contacting of desulfurizing tower circulated sprinkling pipe 12 sprays, mass transfer takes place absorb the SO in the flue gas
2, SO
3And pollutants such as a small amount of remaining HCl, HF and dust are absorbed washing, meet the requirements of to continue behind the desulfuration efficiency upwards, to discharge from desulfurizing tower exhanst gas outlet 14 except the droplet of deentrainment by desulfurizing tower demister 13; Sulfur dioxide concentration in the clean flue gas of discharging is 140mg/Nm
3, dust content is 20mg/Nm
3
The desulfurizing tower absorption liquid is extracted out from desulfurizing tower 10 bottoms by desulfurizing tower circulating pump 11 and is got to desulfurizing tower shower 12, and the spray liquid-gas ratio is 9L/Nm
3Absorption liquid is constantly absorbing SO in the flue gas
2, SO
3, absorption liquid Central Asia ammonium sulfate concentrations can be more and more higher, when ammonium sulfite concentration reaches 35%-40%, gets to oxidation tank 16 near saturated back with desulfurizing tower excavationg pump 15;
Ammoniacal liquor is sent in the desulfurizing tower 10 by aqua ammonia pump 21, and ammoniacal liquor is the ammoniacal liquor of mass concentration 20%, addition 10.1m
3/ h, ammoniacal liquor add in the desulfurizing tower 10 tower prime cement ponds, fully mix with slurries in the tower.Remain between the 5.2-5.8 by the pH value that adds ammoniacal liquor adjusting slurries.
Embodiment 2
The flow process of embodiment 2 and embodiment 1 are identical, and difference is that flue gas is from the steel works sintering machine, and temperature is 120 ℃, and flue gas flow is 1.6 * 10
6Standard cubic meter/hour, sulfur dioxide in flue gas concentration is 1300mg/Nm
3, dust content is 100mg/Nm
3
Be 65mg/Nm by the sulfur dioxide concentration in the clean flue gas of discharging after desulfurizing tower 10 desulfurization
3, dust content is 20mg/Nm
3Finished product chemical fertilizer impurity measurement result is:
Claims (3)
1. effectively remove the ammonia method desulfurizing method of chlorine, fluorine ion and heavy metal ion, it is characterized in that carrying out according to the following steps:
(1), the flue gas that contains sulfur dioxide at first enters the prewashing tower from prewashing tower bottom smoke inlet, the prewashing tower uses industry water and/or recirculated water to make cleaning solution, in tower by prewashing tower circulating pump circulated sprinkling;
(2), flue gas fully contacts the Cl in the flue gas with cleaning solution
-, F
-90-95% is removed, the metal ion of solubility: Fe
3+, Hg
2+, Pb
2+70%-80% is removed, and dust 70%-80% is removed; Along with cleaning solution circulation cleaning in the prewashing tower, the cleaning solution pH value descends gradually, contains mud waste water and additional fresh water by discharging from the tower bed mud slurry outlet of prewashing tower, and the cleaning solution pH value is between 2.2-2.8 in the control prewashing tower;
(3), wash away most Cl
-, F
-With most of Fe
3+, Hg
2+, Pb
2+The flue gas of soluble metal ion and dust leaves the prewashing tower, enters desulfurizing tower after removing droplets entrained by demister;
The mud waste water that contains of (4), discharging at the bottom of the prewashing Tata is delivered to Waste Water Treatment and is handled qualified discharge;
(5), after flue gas enters desulfurizing tower, in desulfurizing tower, flue gas upwards absorbs processing by spraying layer, flue gas is by spraying layer, carries out counter current contacting with the absorption liquid of spray, mass transfer and absorption reaction takes place, to remove the SO in the flue gas
2, SO
3And a small amount of remaining HCl, HF and dust; After flue gas passed spraying layer, the pollutant in the flue gas all removed, and after clean flue gas is removed droplets entrained by demister, discharged outside the tower;
(6), ammoniacal liquor sends in the desulfurizing tower by aqua ammonia pump, ammoniacal liquor adds in the desulfurization Tata prime cement pond, fully mixes with slurries in the tower; Slurries in the tower are ammonium sulfite solutions, and ammonium sulfite solution is by the desulfurizing tower circulating pump, and circulated sprinkling absorbs the SO in the flue gas
2, generate ammonium bisulfite, when the bisulfite ammonium concentration in the slurries was higher, desulfuration efficiency can descend gradually until losing desulphurizing ability fully; By add ammoniacal liquor in the slurries pond, ammoniacal liquor and ammonium bisulfite reaction generate ammonium sulfite, remain between the 5.2-5.8 by the pH value that adds ammoniacal liquor adjusting slurries;
When (7), solution quality concentration reaches 35%-40% in the desulfurizing tower stock tank, by the desulfurizing tower excavationg pump ammonium sulfite solution is got to oxidation tank, be furnished with aeration tube in the oxidation tank, oxidation fan blasts air by aeration tube to the ammonium sulfite solution in the oxidation tank, and making sulfite oxidation is ammonium sulfate;
(8), after the ammonium sulfate of fully oxidation delivers to ammonium sulfate byproduct for treatment system and carry out evaporative crystallization, drying, packing by sulphur ammonium excavationg pump, become qualified agrochemical.
2. the ammonia method desulfurizing method that effectively removes chlorine, fluorine ion and heavy metal ion according to claim 1 is characterized in that: the described employing of prewashing tower void tower, column plate tower or tubulent contact tower.
3. the ammonia method desulfurizing method that effectively removes chlorine, fluorine ion and heavy metal ion according to claim 1 is characterized in that: described ammoniacal liquor is the ammoniacal liquor bought of industrial deposed ammonia, market or uses the liquefied ammonia preparation.
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| CN102423613B true CN102423613B (en) | 2013-10-02 |
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