CN100364647C - Ammonia type flue gas desulfurizing apparatus and its process - Google Patents
Ammonia type flue gas desulfurizing apparatus and its process Download PDFInfo
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- CN100364647C CN100364647C CNB2004100665571A CN200410066557A CN100364647C CN 100364647 C CN100364647 C CN 100364647C CN B2004100665571 A CNB2004100665571 A CN B2004100665571A CN 200410066557 A CN200410066557 A CN 200410066557A CN 100364647 C CN100364647 C CN 100364647C
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- flue gas
- desulfurizing tower
- ammonium sulfate
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Abstract
The present invention discloses an apparatus for desulfurizing flue gas by an ammonia method and a process thereof, which has the advantages of energy saving, stable desulfurization effect and high absorbent utilization rate. The apparatus comprises a desulfurizing tower designed as a counterflow spraying absorption tower, a process water tank, an ammonia water tank and a static mixer, wherein an oxidation pond is arranged at the bottom of the desulfurizing tower, two circulating spraying layers are arranged at the upper part of the desulfurizing tower, two stages of demisters are arranged above the spraying layers, a pre-washing tower is connected with the desulfurizing tower in front in particular, and a separation system of ammonium sulfate is connected with the pre-washing tower. The flue gas enters the pre-washing tower to contact with the saturated solution of (NH4)2SO4, enters the desulfurizing tower after being saturated, cooled, and insulated from heat, flows through the circulating spraying layers from bottom to top and is discharged from the desulfurizing tower after being washed, desulfurized and defogged by the demisters. The solution of ammonium sulfate which evaporates and concentrates because of the hot flue gas in the pre-washing tower is delivered to the separation system of ammonium sulfate and manufactured into the ammonium sulfate product to sell, and the separation filter liquor returns to the pre-washing tower to reconcentrate and recrystallize.
Description
Technical field
The present invention relates to chemical field, specifically, is about a kind of ammonia type flue gas desulfurizing apparatus and technology thereof.
Background technology
At present, employing ammonia is that the flue gas desulfurization technique of absorbent mainly contains two kinds, first kind is to adopt alkaline ammoniacal liquor directly to spray the mode of flue gas on desulfurizing tower top, this technology is because flue-gas temperature is higher, and ammoniacal liquor highly volatile, thereby carry a large amount of free ammonias secretly during fume emission, the sorbent consumption amount is big, the operating cost height.In addition, this desulfur technology at desulfurizing tower middle part because circulated sprinkling flow quantity very few (gas liquid ratio is little), flue-gas temperature reduces less, exit gas temperature is generally about 100 ℃, cause most of reaction product to be discharged with steam, in addition at the bottom of the tower because oxidation unit is not set, its byproduct of ammonium sulfate be difficult to reclaim or the rate of recovery extremely low.
Another kind of sulfur removal technology is that the position with ammonification is arranged on the circulation line, ammoniacal liquor is mixed with circulation fluid afterwards spray flue gas, and this mode is compared with first kind can absorb SO better
2But, make that ammonium sulfate concentrations fails to reach the over-saturation state in the circulating absorption solution, so the recovery technology of outer heating evaporation crystallization has been adopted in the recovery of byproduct of ammonium sulfate because flue-gas temperature is too high, the conventional evaporative crystallization device of one cover need be set on the engineering, have flow process complexity, problem that energy consumption is big.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming and deficiency of existing ammonia type flue gas desulfurizing technology, thereby a kind of novel ammonia type flue gas desulfurizing apparatus is provided.
Another object of the present invention is to provide a kind of ammonia flue gas desulfurization technique.
For reaching above-mentioned purpose, ammonia type flue gas desulfurizing apparatus of the present invention mainly comprises a desulfurizing tower, a technology water tank, an ammoniacal liquor basin and a static mixer, wherein this desulfurizing tower is by reverse-flow spray absorber design, its bottom is an oxidation pond, two-layer circulated sprinkling layer is arranged in this oxidation pond top, and this spraying layer top is provided with the two-stage demister; This technology water tank is connected with the spray header of the demister front and back of desulfurizing tower, and the flushing water and the fume washing water of demister is provided; This ammoniacal liquor basin then is connected with the circulated sprinkling pipe of desulfurizing tower; This static mixer is positioned on the circulated sprinkling pipe, and the oxidation pond with ammoniacal liquor basin and desulfurizing tower is connected respectively; It is characterized in that also be provided with a prewashing column before desulfurizing tower, in addition, prewashing column is connected with the ammonium sulfate piece-rate system again, is used to reclaim byproduct of ammonium sulfate.
According to above device, flue gas desulfurization technique of the present invention is as follows: the flue gas through electrostatic precipitation at first enters prewashing column by gas approach, with the NH from the prewashing column bottom
4)
2SO
4Heat exchange is carried out in saturated solution and stream contact, and flue gas is saturated by thermal insulation, is cooled to 95 ℃～80 ℃, enters desulfurizing tower then; Flue gas flows through the circulated sprinkling layer from bottom to top after entering desulfurizing tower, discharges desulfurizing tower after washing desulphurization, demister demist.And the ammonium sulfate saturated solution in the prewashing column is after carrying out heat exchange with high-temperature flue gas, by further evaporation and concentration, enter the ammonium sulfate piece-rate system, after the cooler cooling, enter the crystallization of crystallisation by cooling groove, obtain the ammonium sulfate finished product then after centrifuge separates, its separating filtrate is sent prewashing column back to.
Ammonia flue gas desulfurization technique of the present invention is owing to be provided with the pre-absorption tower before desulfurizing tower, on the one hand, the heat energy that can make full use of import flue gas itself to the ammonium sulfate near saturation state evaporate, concentrate, crystallization, and do not need additional heat energy, reach purpose of energy saving; On the other hand, because circulation fluid is in critical saturation state all the time in the desulfurizing tower, guaranteed the stability of circulating absorption solution desulfurized effect.And because of having utilized the ammonium sulfate piece-rate system that is connected with prewashing column as recovery system, recovery technology is easy and cost recovery is low.
Description of drawings
Figure one is the system flow chart of ammonia type flue gas desulfurizing technology of the present invention and technology thereof.
The specific embodiment
Below in conjunction with accompanying drawing, structure composition of the present invention, technological means and function are described further:
As shown in Figure 1, flue gas desulfur device of the present invention mainly comprises a desulfurizing tower 2, a technology water tank 7, an ammoniacal liquor basin 8 and a static mixer 9, this desulfurizing tower 2 is by reverse-flow spray absorber design, desulfurizing tower 2 bottoms are oxidation pond 3, two-layer circulated sprinkling layer 4 is arranged in these oxidation pond 3 tops, and these spraying layer 4 tops are provided with two-stage demister 5; This technology water tank 7 is connected with the spray header 11 of demister 5 front and back of desulfurizing tower 2, and the flushing water and the fume washing water of demister 5 is provided; Ammoniacal liquor basin 8 then is connected with the circulated sprinkling pipe 10 of desulfurizing tower 2; This static mixer 9 is positioned on the circulated sprinkling pipe 10, and the oxidation pond 3 with ammoniacal liquor basin 8 and desulfurizing tower 2 is connected respectively; Feature of the present invention is to be provided with a prewashing column 1 before desulfurizing tower 2, and this prewashing column 1 bottom links to each other with the oxidation pond 3 of an ammonium sulfate piece-rate system 6 with desulfurizing tower 2 bottoms respectively.
Boiler smoke through electrostatic precipitation enters prewashing column 1 by gas approach.In prewashing column 1,135 ℃～140 ℃ hot flue gas with contact from the ammonium sulfate saturated solution of prewashing column 1 bottom and stream, carry out heat exchange, the flue gas heat release, temperature is expelled to desulfurizing tower 2 after dropping to 95 ℃～80 ℃; Ammonium sulfate supersaturated solution (main component is 5%～10% ammonium sulfate crystallization and a small amount of flue dust) because of hot flue gas evaporation and concentration is sent to ammonium sulfate piece-rate system 6 simultaneously, makes the ammonium sulfate finished product and sells, and its separating filtrate is sent prewashing column 1 back to.The pH of prewashing column circulation fluid ammonium sulfate is lower, generally below pH4, and when the pH of solution is between 4.2～7.0, and free ammonia and SO in the solution
2Therefore concentration is all very low, almost can ignore, and the pH value of taking out from prewashing column 1 is the effusion problem that there is not ammonia in ammonium sulfate concentrate below 4, greatly reduces the consumption of raw material ammonia.
Enter desulfurizing tower 2 behind the flue gas cool-down and carry out desulphurization reaction, flue gas flows through circulated sprinkling layer 4 from bottom to top, discharges desulfurizing tower 2 after washing desulphurization, demister 5 demists.
When 95 ℃～80 ℃ flue gases pass through circulated sprinkling layer 4, fully saturated by the water of spray liquid, and be cooled to adiabatic saturation temperature, and be about 55 ℃～60 ℃, finish desulphurization reaction.This spray liquid mainly comprises from the circulation fluid (NH in the fresh water (FW) of technology water tank 7 and the circulated sprinkling pipe 10
4HSO
3, (NH
4)
2SO
4, (NH
4)
2SO
3And NH
3The mixed solution of water).From the ammoniacal liquor of 20% concentration in the ammoniacal liquor basin 8 and NH from oxidation pond at the bottom of the desulfurizing tower 3
4HSO
3(NH
4)
2SO
4Mixed liquor in circulated sprinkling pipe 10, mix by static mixer 9, enter desulfurizing tower 2 sprays then and absorb flue gases, the reaction equation of this process is:
NH
3+NH
4HSO
3＝(NH
4)
2SO
3
SO
2+(NH
4)
2SO
3+H
2O＝2NH
4HSO
3
Flue gas after the desulfurization is through demister 5 demists, and most droplets of carrying secretly in the flue gas after the separated and collected spray absorbs make exhanst gas outlet droplet content＜100mg/Nm
3, enter chimney at last.Spray header 11 is installed in the front and back of each demister 5 element, use fresh water (FW) regularly to wash from fresh water (FW) case 7, remove demister 5 lip-deep sediments, the moisture content that replenishment cycles liquid is taken away because of flue gas is saturated, keep liquid level at the bottom of the tower, level chain at the bottom of water regulating valve and the tower (conventional means in the existing flue gas desulfurization technique).
In the desulphurization reaction in desulfurizing tower 2, (the NH that reaction generates
4)
2SO
3With minor N H
4HSO
3With the oxidation pond 3 at the bottom of the circulation fluid inflow tower.At 3 ends of oxidation pond high-efficiency aerator 12 is housed, sends into oxidation air, impel ammonium sulfite (NH from compressed air oxidation pond 3 at the bottom of the absorption tower of power plant's air compression station
4)
2SO
3Be oxidized to ammonium sulfate (NH
4)
2SO
4, reaction equation is:
(NH
4)
2SO
3+1/2O
2＝(NH
4)
2SO
4。
Make in the bubbling oxidation that solid particle is in the suspension flow regime in the slurries, prevent precipitation.
The oxidation pond 3 of desulfurizing tower 2 links to each other with prewashing column 1 bottom, and prewashing column 1 links to each other with ammonium sulfate piece-rate system 6, just constitutes the circulation of whole system ammonium sulfate thus.
The ammonium sulfate piece-rate system 6 of joining with prewashing column 1: this ammonium sulfate piece-rate system 6 is made of a cooler 16, crystallisation by cooling groove 17 and centrifuge 18.In the desulphurization reaction in desulfurizing tower 2, SO in the flue gas
2With the ammoniacal liquor reaction, the reaction by-product of its generation is an ammonium sulfate.This ammonium sulfate enters prewashing column 1 by oxidation pond 3 bottoms of desulfurizing tower 2, concentrate with the hot smoke evaporative of import, (main component is an ammonium sulfate crystallization to the concentrate of its generation, contain a small amount of flue dust simultaneously) enter ammonium sulfate piece-rate system 6, with the taking-up liquid pump slurries are beaten to cooler 16 coolings earlier and entered 17 crystallizations of crystallisation by cooling groove, make the sulphur ammonium product then after centrifuge 18 liquid-solid separation, the hot flue gas that its separating filtrate is sent prewashing column 1 and import back to carries out condensing crystallizing again.
The ammonification position of this device is selected on the circulated sprinkling pipe 10, the addition of ammonia is by the pH value control (conventional means in the existing flue gas desulfurization technique) of static mixer 9 back solution, can regulate the amount that adds ammoniacal liquor or liquefied ammonia automatically, keep in the oxidation pond 3 of desulfurizing tower 2 circulating absorption solution pH between 5.5～6.5, thereby make SO in the circulated sprinkling pipe 10
2The pH value of absorption liquid is higher, and desulfuration efficiency remains at a higher level, and the pH value of the absorption liquid of oxidation pond 3 is lower, and the crystallization that is beneficial to ammonium sulfate is reclaimed.
Import and export at desulfurizer respectively is provided with 1 two baffle plates isolation air door 13,14, establishes one and can regulate by-pass damper door 15 on the bypass flue.When desulphurization system maybe needed to overhaul as accident occurring, the two baffle plates isolation of desulphurization system import and export air door 13,14 was closed, and the by-pass damper door 15 of flue collector is opened.Boiler smoke can directly enter chimney and discharge through the by-pass damper door 15 of flue collector.And the absorption slurries in the desulfurizing tower 2 enter in the technology tank (emptying in advance), so that desulfurizing tower 2 is keeped in repair.
In sum, the present invention is provided with a prewashing column before desulfurizing tower, to flue gas washing, cooling, utilize the heat energy of flue gas self to make the absorption liquid condensing crystallizing, thereby reach purpose of energy saving, and make desulfurized effect stable and sorbent utilization is high, because of having utilized the ammonium sulfate piece-rate system that is connected with prewashing column as recovery system, recovery technology is easy and cost recovery is low simultaneously.
Claims (9)
1. ammonia type flue gas desulfurizing apparatus, comprise a prewashing column, a desulfurizing tower, a technology water tank and an ammoniacal liquor basin, described prewashing column is arranged at before the described desulfurizing tower, described desulfurizing tower is by reverse-flow spray absorber design, and the desulfurizing tower bottom is an oxidation pond, it is characterized in that, also comprise a static mixer, wherein, described oxidation pond top is furnished with the circulated sprinkling layer, and this spraying layer top is provided with demister; Be provided with one deck water spraying layer between demister and the spraying layer, can prevent the escape of ammonia; The desulfurizing agent feed system adopts the ammoniacal liquor system; Described technology water tank is connected with the spray header of the demister front and back of described desulfurizing tower; Described ammoniacal liquor basin then is connected with the circulated sprinkling pipe of desulfurizing tower; Described static mixer is positioned on the circulation fluid pipe, and the oxidation pond with described ammoniacal liquor basin and described desulfurizing tower bottom is connected respectively.
2. ammonia type flue gas desulfurizing apparatus according to claim 1 is characterized in that described demister is equipped with two-stage.
3. ammonia type flue gas desulfurizing apparatus according to claim 1 is characterized in that, spray header is installed in the front and back of described demister.
4. ammonia type flue gas desulfurizing apparatus according to claim 1 is characterized in that, at the bottom of the described oxidation pond high-efficiency aerator is installed.
5. according to each described ammonia type flue gas desulfurizing apparatus in the claim 1～4, it is characterized in that described prewashing column also is connected with an ammonium sulfate piece-rate system.
6. ammonia type flue gas desulfurizing apparatus according to claim 5 is characterized in that, described ammonium sulfate piece-rate system is made of a cooler, a crystallisation by cooling groove and a centrifuge.
7. ammonia flue gas desulfurization technique based on each described device among the claim 1-6, it is characterized in that may further comprise the steps: after hot flue gas enters prewashing column, with the ammonium sulfate saturated solution and stream contact, flue gas is saturated by thermal insulation, after cooling off to desulfurizing tower; Flue gas flows through the circulated sprinkling layer from bottom to top in desulfurizing tower, and is fully saturated by the water in the sprayed slurry, and is cooled to adiabatic saturation temperature, finishes desulphurization reaction, after the demister demist, enters chimney.
8. ammonia flue gas desulfurization technique according to claim 7 is characterized in that, also comprises the recycling step of ammonium sulfate.
9. ammonia flue gas desulfurization technique according to claim 8, it is characterized in that, the recycling step of described ammonium sulfate comprises: the ammonium sulfate supersaturated solution in the prewashing column is beaten to the cooler cooling by liquid pump, enter the crystallization of crystallisation by cooling groove, separate obtaining finished product ammonium sulfate then through centrifuge, its separating filtrate is sent prewashing column back to and is carried out condensing crystallizing again.
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| CNB2004100665571A CN100364647C (en) | 2004-09-22 | 2004-09-22 | Ammonia type flue gas desulfurizing apparatus and its process |
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|---|---|---|---|
| CNB2004100665571A CN100364647C (en) | 2004-09-22 | 2004-09-22 | Ammonia type flue gas desulfurizing apparatus and its process |
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| CN100364647C true CN100364647C (en) | 2008-01-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780368A (en) * | 2010-03-26 | 2010-07-21 | 张蕊 | Low energy consumption flue gas wet desulphurization process |
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-
2004
- 2004-09-22 CN CNB2004100665571A patent/CN100364647C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983217A (en) * | 1973-09-26 | 1976-09-28 | Kurashiki Boseki Kabushiki Kaisha | Method for removing sulfur dioxide from waste gases |
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| US5362458A (en) * | 1993-03-22 | 1994-11-08 | General Electric Environmental Services, Incorporated | Process for the simultaneous absorption of sulfur oxides and production of ammonium sulfate |
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| CN101780368A (en) * | 2010-03-26 | 2010-07-21 | 张蕊 | Low energy consumption flue gas wet desulphurization process |
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