CN101879406B - Dual-alkali flue gas desulfurization device and desulfurization method - Google Patents

Dual-alkali flue gas desulfurization device and desulfurization method Download PDF

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CN101879406B
CN101879406B CN 201010226988 CN201010226988A CN101879406B CN 101879406 B CN101879406 B CN 101879406B CN 201010226988 CN201010226988 CN 201010226988 CN 201010226988 A CN201010226988 A CN 201010226988A CN 101879406 B CN101879406 B CN 101879406B
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absorption tower
dual
flue gas
tank
oxidation
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CN101879406A (en
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陈公卫
杨恒凯
陆阳
刘军
马继德
张新
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Coal Industry Jinan Design & Research Co Ltd
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Coal Industry Jinan Design & Research Co Ltd
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Abstract

The invention relates to a dual-alkali flue gas desulfurization device and a desulfurization method. The dual-alkali flue gas desulfurization device comprises an absorption tower, a liquid alkali storage tank and a quick lime powder cabin, wherein the quick lime powder cabin is communicated with a lime slurry tank, an oxidation recovery tank, a primary sedimentation tank, a secondary sedimentation tank and a circulating tank in turn; the bottom of the absorption tower is provided with pipes leading to the oxidation recovery tank, the secondary sedimentation tank and the circulating tank; and an absorption tower circulating pump leading to the upper part of the absorption tower is arranged in the circulating tank. The desulfurization process comprises the following steps of: pumping NaOH solution into the absorption tower by using a pump to fully contact a flue gas so as to ensure that sulfur dioxide reacts with NaOH to produce NaHSO3 solution; discharging the NaHSO3 solution into the oxidation recovery tank from the absorption tower; simultaneously, adding Ca(OH)2 slurry into the oxidation recovery tank to produce the calcium sulfite precipitate; and producing a CaSO4 sediment through an oxidation effect of the air provided by an oxidation blower. The device and the method have the advantages of completely eliminating the possibility of fouling and blocking in the tower, having high desulfurization efficiency and low operating cost and preventing huge waste of a desulfurizing agent.

Description

A kind of dual-alkali flue gas desulfurization device and sulfur method
(1) technical field
The present invention relates to a kind of dual-alkali flue gas desulfurization device and sulfur method, belong to the atmospheric environment protection technical field.
(2) background technology
At present, the large-sized boiler equipment desulfurization project capital construction of China coal-burning power plant finishes, and most of professional desulfurization company turns to sight the flue gas desulfurization of Pump for Medium and Small Power Generating Set.Also in constantly developing, double alkali method desulfurizing technology is with its desulfuration efficiency height for the sulfur removal technology of Pump for Medium and Small Power Generating Set, and the advantage that operating cost is low is occupied very big proportion on market.
But, by to the follow-up investigation of double alkali method desulfurizing project in recent years, find through long-time running, fouling in the double alkali method desulfurizing technology ubiquity absorption tower, the sodium sulfite unsuccessful shortcoming of regenerating causes manufacturing enterprise in order to reach desulfurized effect, rolls up the input of NaOH, increased cost greatly simultaneously because sodium sulfite regeneration is unsuccessful, and made desulfuration efficiency can't maintain the level of a higher stable.
(3) summary of the invention
The present invention provides a kind of desulfuration efficiency height in order to remedy the deficiencies in the prior art, and parallel-adder settle-out time is long, and operating cost is low, can avoid the huge waste of desulfurizing agent and prevent dual-alkali flue gas desulfurization device and the sulfur method that fouling is stopped up in the absorption tower.
The present invention is achieved through the following technical solutions:
A kind of dual-alkali flue gas desulfurization device, comprise absorption tower, liquid caustic soda storage tank, calcium lime powder storehouse, it is characterized in that: described calcium lime powder storehouse is communicated with lime stock tank, oxidation regeneration pond, one-level sedimentation basin, second-level settling pond and circulatory pool successively, the bottom on absorption tower is provided with the pipeline that leads to oxidation regeneration pond, second-level settling pond and circulatory pool respectively, circulatory pool is provided with the absorption tower circulating pump that leads to top, absorption tower, and the outlet at bottom of one-level sedimentation basin, second-level settling pond leads to horizontal vacuum belt filter by the gypsum deslagging pump.
Dual-alkali flue gas desulfurization device of the present invention, described oxidation regeneration pond is connected with oxidation fan; Be provided with agitator tank between described one-level sedimentation basin and the second-level settling pond.
Dual alkali scrubbing FGD process method of the present invention is characterized in that: comprise the steps: 1) pulverized limestone slurrying, NaOH is made solution; 2) in the absorption tower, wash flue gas with sodium hydroxide solution, remove the SO in the flue gas 23) the oxidation regeneration pond outside the absorption tower will absorb SO 2Acidic circulation liquid mix with aqua calcis; Simultaneously in the oxidation regeneration pond, blast air; 4) slurries that will handle enter the one-level sedimentation basin and precipitate, and mainly generating sediment is calcium sulfate; 5) through the one-level post precipitation, the clear liquid of generation enters second-level settling pond and continues precipitation, and main product is a calcium sulfite; 6) two-stage post precipitation is discharged by the precipitation of slag stock pump at the bottom of with sedimentation basin, sends into the vacuum belt dewaterer dehydration, makes the filter cake outward transport; The second-level settling pond supernatant is got back to circulatory pool, pumps into the absorption tower by circulating pump and continues to absorb sulfur in smoke.
Dual alkali scrubbing FGD process method of the present invention, the Na ion concentration of circulation fluid is not less than 0.3 mol in the circulatory pool; Discharge opeing exports SO at the bottom of absorbing Tata 2The pH value of acidic circulation liquid be 5~6; The mass percent concentration of described sodium hydroxide solution is 20-30%, and the mass percent concentration of aqua calcis is 10-30%; The magnitude of recruitment of NaOH is SO by the ratio of amount in unit interval 25% for the treatment of capacity: the magnitude of recruitment of unit interval sodalime powder is SO by the ratio of amount 21.03 for the treatment of capacity.
Dual-alkali flue gas desulfurization device of the present invention and sulfur method, the technology that it adopts is the tower external circulation process, be that absorption tower and circulatory pool separate, the circulation liquid pool of circulating pump outside being arranged on tower extracts circulation fluid and sprays in the tower, and flue gas rises in the tower to contact to wash with circulation fluid and removes sulfur dioxide.What double alkali method desulfurizing technology of the present invention adopted is the two-stage sedimentation basin, and from a structural point, the two-stage sedimentation basin is all the vertical sedimentation basin structure, this class formation floor space is little, deposition efficiency height, high energy guarantee to handle 200 cubic metres in one hour, and concentration is 30% slurries.The two-stage sedimentation basin of double alkali method desulfurizing technology of the present invention on function, the sediment difference that removes, one-level sedimentation basin deposit is mainly gypsum, just calcium sulfate; The deposit that second-level settling pond removes is a calcium sulfite.Double alkali method desulfurizing technology two-stage sedimentation basin of the present invention belongs to the front and back operation that slurries are handled respectively, the sedimentation basin volume is identical, sediment more than 85% (calcium sulfate) promptly can be removed at the one-level sedimentation basin, and remaining 15% sediment (calcium sulfite) is removed at second-level settling pond.
Main points of the present invention are the control to circulation fluid pH value and desulfurization absorbent feeding coal, the pH value that should guarantee absorption tower outlet circulation fluid within the specific limits, the quantity delivered that guarantees lime slurry again can not be too high, otherwise cause the waste of desulfurizing agent to cause desulphurization cost to increase easily.The main effect of sodium hydroxide solution is to guarantee that environment has enough sodas to participate in reaction in the whole system tower, prevent that calcium ion from causing that fouling is stopped up in the tower, the main exhaustion point of sodium ion is the content in the moisture of being taken away by gypsum deposition, is about SO by the ratio of amount 25%.Sulfur removal technology adopts the reaction tank of oxidation regeneration integrative-structure, because oxidation is gas liquid reaction, reaction speed is slower, and regenerative response is to react between liquid ions, and reaction speed is very fast.It is lower that sulfur removal technology removes absorption tower outlet circulatory pool circulation fluid pH value, other regional slurries ponds comprise oxidation regeneration pond, one-level sedimentation basin, second-level settling pond, lime white liquid pool and liquid caustic soda jar pH value all above more than 12, and absorption tower outlet circulation fluid pH value is a key control parameter.If agitator tank is not set, can directly circulation fluid in the tower be drawn one the tunnel and add second-level settling pond central tube position between the two-stage sedimentation basin; If between the two-stage sedimentation basin, agitator tank is set, then come liquid to mix circulation fluid adding agitator tank and one-level sedimentation basin in the tower, promote the calcium ion precipitation.Sulfur removal technology adopts the nucleus equipment of horizontal vacuum formula belt feeder as the gypsum treatment system, than the plate and frame filtering equipment with drag for slag equipment, reduces the gypsum moisture content greatly, improves the utilization rate of NaOH.
The present invention has overcome the shortcoming that traditional double alkali method desulfurizing technology regeneration stage calcium ion components is difficult to remove, changing the stock tank stage of reaction in the traditional handicraft tower into tower simultaneously reacts outward, eliminated the possibility that fouling is stopped up in the tower fully, and desulfuration efficiency height, operating cost is low, can avoid the huge waste of desulfurizing agent.Guarantee that whole desulphurization system long-term stability moves efficiently.
(4) description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is the schematic diagram of dual-alkali flue gas desulfurization device of the present invention and sulfur method.
Among the figure, 1 is the absorption tower, 2 oxidation regeneration ponds, 3 one-level sedimentation basins, 4 second-level settling ponds, 5 circulatory pools, 6 absorption tower circulating pumps, 7 gypsum deslagging pumps, 8 horizontal vacuum belt filters, 9 oxidation fans, 10 liquid caustic soda storage tanks, 11 calcium lime powder storehouses, 12 lime stock tanks.
(5) specific embodiment
Accompanying drawing is a kind of specific embodiment of the present invention.This embodiment comprises absorption tower 1, liquid caustic soda storage tank 10, calcium lime powder storehouse 11, calcium lime powder storehouse 11 is communicated with lime stock tank 12, oxidation regeneration pond 2, one-level sedimentation basin 3, second-level settling pond 4 and circulatory pool 5 successively, the bottom on absorption tower 1 is provided with the pipeline that leads to oxidation regeneration pond 2, second-level settling pond 4 and circulatory pool 5 respectively, circulatory pool 5 is provided with the absorption tower circulating pump 6 that leads to 1 top, absorption tower, and the outlet at bottom of one-level sedimentation basin 3, second-level settling pond 4 leads to horizontal vacuum belt filter 8 by gypsum deslagging pump 7; Oxidation regeneration pond 2 is connected with oxidation fan 9; Be provided with agitator tank between one-level sedimentation basin 3 and the second-level settling pond 4.
Dual-alkali flue gas desulfurization device mainly comprises following subsystem: A) absorbent preparation system comprises liquid caustic soda storage tank 10, calcium lime powder storehouse 11 and lime stock tank 12; B) sulfur dioxide absorption system comprises desulfuration absorbing tower 1, circulatory pool 5 and absorption tower circulating pump 6; C) desulfurization product treatment system comprises oxidation regeneration pond 2, one-level sedimentation basin 3, second-level settling pond 4, gypsum deslagging pump 7, horizontal vacuum belt filter 8, oxidation fan 9.
Dual alkali scrubbing FGD process method of the present invention, adopt following steps: 1) pulverized limestone slurrying, NaOH is made solution; 2) in the absorption tower, wash flue gas with sodium hydroxide solution, remove the SO in the flue gas 23) the oxidation regeneration pond outside the absorption tower will absorb SO 2Acidic circulation liquid mix with aqua calcis; Simultaneously in the oxidation regeneration pond, blast air; 4) slurries that will handle enter the one-level sedimentation basin and precipitate, and mainly generating sediment is calcium sulfate; 5) through the one-level post precipitation, the clear liquid of generation enters second-level settling pond and continues precipitation, and main product is a calcium sulfite; 6) two-stage post precipitation is discharged by the precipitation of slag stock pump at the bottom of with sedimentation basin, sends into the vacuum belt dewaterer dehydration, makes the filter cake outward transport; The second-level settling pond supernatant is got back to circulatory pool, pumps into the absorption tower by circulating pump and continues to absorb sulfur in smoke.
This sulfur removal technology adopts Ca (OH) 2With NaOH as desulfurization absorbent, at first NaOH solution is squeezed into the absorption tower through pump and fully contacts with flue gas, NaOH in sulfur in smoke and the desulfurizing agent is reacted generates NaHSO 3Solution, NaHSO 3Solution is discharged from the absorption tower and is entered the oxidation regeneration pond, adds Ca (OH) simultaneously in the oxidation regeneration pond 2Slurries, reaction generates CaSO 3And Na 2SO 3, CaSO 3Through the air blast oxidation, generate CaSO 4Sediment, through two-stage sedimentation basin precipitation, clear liquid is sent into circulatory pool, makes gypsum filter cake after sediment further dewaters and abandons, and filtrate is reclaimed, and turns back to circulatory pool and utilizes again.
Tower outer circulation two-stage precipitation double alkali method desulfurizing technology of the present invention, at first the powder tank car ships the above outsourcing calcium lime powder of 200 orders and sends into calcium lime powder storehouse 11 outside the factory, add pulverized limestone by the metering device that is located at 11 bottoms, calcium lime powder storehouse to lime stock tank 12, by control, make the Ca that mass percent concentration is 10-30% (OH) to plant area's fresh water (FW) addition 2Solution; By liquid caustic soda tank car outside the factory outsourcing liquid caustic soda is sent into liquid caustic soda storage tank 10.
When system just moves, in circulatory pool 5, at first be mixed with the sodium hydroxide solution that mass percent concentration is 20-30%, the volume of circulatory pool 5 will guarantee to reach under the condition of 5 liters/standard cubic meter at liquid-gas ratio, 5~8 minutes plasma discharge amount when absorption tower circulating pump 6 is all opened; For guaranteeing that system reaches the stably desulphurizing operational effect, whenever Na ion concentration all must not be lower than 0.3 mol to the circulation fluid in the circulatory pool 5.
When the sulfur-containing smoke gas, open absorption tower circulating pump 6 and extract sodium hydroxide solution in circulatory pool in the absorption tower, the spraying layer that is provided with by circulating line and Ta Nei sprays circulation fluid and carries out desulfurization in the absorption tower.The pH value of discharge opeing outlet is in 5~6 level at the bottom of the control tower, makes that main component is a sodium hydrogensulfite in the circulation fluid of discharging at the bottom of the tower.
Solution of sodium bisulfite enters oxidation regeneration pond 2, add lime white simultaneously, by the agitator stirring action in the pond, reaction generates the calcium sulfite precipitation, so, in oxidation regeneration pond 2, blast a large amount of air by oxidation fan 9 simultaneously calcium sulfite oxidation become calcium sulfate precipitation because the stirring action precipitation can not be deposited to the bottom in oxidation regeneration pond 2.
Calcium sulfate mixed serum in the oxidation regeneration pond 2 enters one-level sedimentation basin 3, pass through precipitation, form the calcium sulfate precipitation layer at slag bucket place, one-level sedimentation basin 3 bottom, the suction inlet of gypsum deslagging pump 7 is established in one-level sedimentation basin 3 bottoms, in time calcium sulfate precipitation is extracted out and be sent to horizontal vacuum belt filter 8, filter the gypsum filter cake outward transport of back generation through belt feeder and abandon, it is recycling that the filtrate of belt feeder is returned circulatory pool.
Through after the precipitation, supernatant is mainly the mixed solution of NaOH and calcium hydroxide at one-level sedimentation basin 3.The calcium ion concentration of dissolving wherein is still higher, is the main cause that causes fouling in the absorption tower, therefore, needs further to remove calcium ion, at utmost reduces the possible factor of fouling.
The supernatant of one-level sedimentation basin 3 post precipitations enters second-level settling pond 4, draw one road circulation fluid from the absorption tower leakage fluid dram simultaneously and feed second-level settling pond 4, because the circulation fluid Main Ingredients and Appearance that leakage fluid dram is discharged is a sodium hydrogensulfite, therefore can cause inferior sulfate radical excessive, further the calcium ion of calcium hydroxide can be removed.
Through behind the two-stage precipitation, main component is a sodium sulphate in the clear liquid, sodium sulfite and NaOH, and clear liquid enters circulatory pool 5 then, finishes the once desulfurization cyclic process.

Claims (8)

1. dual-alkali flue gas desulfurization device, comprise absorption tower (1), liquid caustic soda storage tank (10), calcium lime powder storehouse (11), it is characterized in that: described calcium lime powder storehouse (11) is communicated with lime stock tank (12) successively, oxidation regeneration pond (2), one-level sedimentation basin (3), second-level settling pond (4) and circulatory pool (5), the bottom on absorption tower (1) is provided with leads to oxidation regeneration pond (2) respectively, the pipeline of second-level settling pond (4) and circulatory pool (5), circulatory pool (5) is provided with the absorption tower circulating pump (6) that leads to top, absorption tower (1), one-level sedimentation basin (3), the outlet at bottom of second-level settling pond (4) leads to horizontal vacuum belt filter (8) by gypsum deslagging pump (7); Liquid caustic soda storage tank (10) is communicated with oxidation regeneration pond (2).
2. dual-alkali flue gas desulfurization device according to claim 1 is characterized in that: described oxidation regeneration pond (2) is connected with oxidation fan (9).
3. dual-alkali flue gas desulfurization device according to claim 1 is characterized in that: be provided with agitator tank between described one-level sedimentation basin (3) and the second-level settling pond (4).
4. adopt the dual alkali scrubbing FGD process method of the described dual-alkali flue gas desulfurization device of claim 1, it is characterized in that: comprise the steps: 1) pulverized limestone slurrying, NaOH is made solution; 2) in the absorption tower, wash flue gas with sodium hydroxide solution, remove the SO in the flue gas 23) the oxidation regeneration pond outside the absorption tower will absorb SO 2Acidic circulation liquid mix with aqua calcis; Simultaneously in the oxidation regeneration pond, blast air; 4) slurries that will handle enter the one-level sedimentation basin and precipitate, and mainly generating sediment is calcium sulfate; 5) through the one-level post precipitation, the clear liquid of generation enters second-level settling pond and continues precipitation, and main product is a calcium sulfite; 6) two-stage post precipitation is discharged by the precipitation of gypsum deslagging pump at the bottom of with sedimentation basin, sends into the dehydration of horizontal vacuum belt filter, makes the filter cake outward transport; The second-level settling pond supernatant is got back to circulatory pool, pumps into the absorption tower by circulating pump and continues to absorb sulfur in smoke.
5. dual alkali scrubbing FGD process method according to claim 4 is characterized in that: the Na ion concentration of circulation fluid is not less than 0.3 mol in the circulatory pool.
6. dual alkali scrubbing FGD process method according to claim 4 is characterized in that: discharge opeing exports SO at the bottom of absorbing Tata 2The pH value of acidic circulation liquid be 5~6.
7. dual alkali scrubbing FGD process method according to claim 4 is characterized in that: the mass percent concentration of described sodium hydroxide solution is 20-30%, and the mass percent concentration of aqua calcis is 10-30%.
8. dual alkali scrubbing FGD process method according to claim 4 is characterized in that: the magnitude of recruitment of NaOH is SO by the ratio of amount in the unit interval 25% for the treatment of capacity, the magnitude of recruitment of unit interval sodalime powder is SO by the ratio of amount 21.03 for the treatment of capacity.
CN 201010226988 2010-07-15 2010-07-15 Dual-alkali flue gas desulfurization device and desulfurization method Expired - Fee Related CN101879406B (en)

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