CN1162206C - Smoke discharging desulphurization device - Google Patents
Smoke discharging desulphurization device Download PDFInfo
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- CN1162206C CN1162206C CNB00101918XA CN00101918A CN1162206C CN 1162206 C CN1162206 C CN 1162206C CN B00101918X A CNB00101918X A CN B00101918XA CN 00101918 A CN00101918 A CN 00101918A CN 1162206 C CN1162206 C CN 1162206C
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- mentioned
- sulphur ammonium
- liquid
- ammonium sulfate
- ammonium
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Abstract
To reduce the product cost of ammonium sulfate by discharging a part of separated liq., lowering its quantity and also improving a recovering efficiency of the ammonium sulfate moreover to improve a product value of the ammonium sulfate by preventing the inclusion of soot and dust and heavy metal to the ammonium sulfate to be recovered. In this desulfurization equipment, a filter for separating solid matter, a crystallization can for precipitating the ammonium sulfate, a separator for separating the separated ammonium sulfate and a return line for returning the separated liq. separated at the separator to the crystallization can are provided from upstream side at an ammonium sulfate recovering line for discharging an ammonium sulfate soln. Then, the flue gas is discharged to the outside of system so that the conc. of ammonium chloride in the separated liq. is not more than combined solubility by supplying a pH adjusting soln. to the upstream side of the filter.
Description
Technical field
The present invention relates to flue gas desulfurization equipment, relate to specifically with the sulfur dioxide in the ammonia absorption smoke evacuation, and then recovery is as the wet type ammonia desulfurizer of accessory substance ammonium sulfate (sulphur ammonium).
Background technology
For coal-burning boiler,, and be contained in the discharging gas of discharge these nitrogen oxide NO owing to the burning of the nitrogen in the fuel, sulphur produces nitrogen oxide and sulfur oxide
xWith sulfur oxide SO
x(major part is SO
2) cause atmosphere pollution, so, in the exhausted smoke processing system of coal-burning boiler device, be provided for removing the nitrogen rejection facility of nitrogen oxide, and the desulfurizer that is used to remove sulfur oxide.
In Fig. 2, roughly the exhausted smoke processing system to the coal-burning boiler device is illustrated.
From the waste gas that coal-burning boiler 1 is discharged, remove nitrogen oxide with nitrogen rejection facility 2.Discharging gas by these nitrogen rejection facility 2 back discharges, with air preheater 3, with the burning usefulness air carry out heat exchange, the air that heating flame is used, pass through gas hot-air heater (heat regenerator) 4 backs again by electrostatic (electric dust) precipitator 5, in the process process of this electrostatic (electric dust) precipitator 5, remove solid matters such as coal dust.With air exhauster 6, the discharging pneumatic transmission that comes out from this electrostatic (electric dust) precipitator 5 to desulfurizer 7.Removed the discharging gas behind the sulfur oxide with this desulfurizer 7, heat with gas hot-air heater (reheater) 8.Discharging gas coming out from this gas hot-air heater 8 boosts with ventilation blower 9, enters atmosphere from chimney 10.Among the figure, the 11st, be used to carry the compressor fan of combustion air.Also have,, can omit above-mentioned gas hot-air heater 4 gentle hot-air heaters 8, the discharging gas from desulfurizer 7 is directly discharged from chimney 10 according to the scale of coal-burning boiler device.
With the occasion of ammonia, generate ammonium sulfate (sulphur ammonium) as byproduct of reaction as the sulfur oxide absorbent of above-mentioned desulfurizer 7.
With Fig. 3 above-mentioned original desulfurizer 7 is illustrated.
From the discharging conductance of above-mentioned electrostatic (electric dust) precipitator 5 to absorption tower 12, absorption liquid 15 is stored in the bottom on above-mentioned absorption tower 12.By absorption liquid circulating pump 16 this absorption liquid 15 is drunk up, and in above-mentioned absorption tower 12, scatter.In the circulation way of the absorption liquid that adopts above-mentioned absorption liquid circulating pump 16,,, suitably replenish from ammoniacal liquor source of supply 18, so that the ammonia concentration of above-mentioned absorption liquid 15 maintains in the predetermined scope through this ammoniacal liquor supply line 17 with ammoniacal liquor supply line 17 interflow.
In above-mentioned absorption tower 12, scatter ammoniacal liquor, make the SO in the discharging gas
2Gas carries out gas-liquid with ammoniacal liquor and contacts, by the desulphurization reaction of representing with following formula: (
), from discharging gas, absorb SO
2Gas.(the NH that in above-mentioned desulphurization reaction, generates
4)
2SO
3(ammonium sulfite) reaches concentration predetermined value in the above-mentioned absorption liquid 15 when above, and the absorption liquid of part circulation is sent into oxidizing tower 20, is stored in the bottom of this oxidizing tower 20.The air 21 that oxidation is used is blown in the ammonium sulfite concentrate of storage, by oxidation reaction (
) generation (NH
4)
2SO
4(sulphur ammonium).Reacted surplus air in the above-mentioned oxidizing tower 20 turns back in the above-mentioned absorption tower 12, discharges from above-mentioned chimney 10 with discharging gas.
The ammonium sulfate solution 24 of dissolve sulfur ammonium is extracted out from above-mentioned oxidizing tower 20 with delivery pump 22, sends into crystallizing tank 25.In this crystallizing tank 25 with steam 26 as thermal source, the water evaporates of sulphur ammonium lysate 24.By evaporation, the sulphur ammonium concentration in the liquid is improved, the sulphur ammonium is separated out.The sulphur ammonium slurry of extracting out from above-mentioned crystallizing tank 25, deliver in the seperator 27, with this seperator 27 solid-state sulphur ammonium 28 is separated.Liquid after separating is partly returned and is back in the above-mentioned crystallizing tank 25 by pipeline 29.
The hydrogen chloride (HCl) that contains trace in the bunker coal of coal-burning boiler 1 when absorbing sulfur dioxide with ammoniacal liquor, generates ammonium chloride (oronain, NH
4Cl).From above-mentioned sulphur ammonium lysate 24, separate out the sulphur ammonium, so oronain concentration rises.When the oronain of separating out is sneaked in the sulphur ammonium, the purity of sulphur ammonium is reduced, the commodity value of sulphur ammonium is descended.Contained impurity is concentrated in the liquid component that aforesaid in addition seperator 27 is separated, and then the crystal of sulphur ammonium has been separated out harmful effect, can't be recovered to the sulphur ammonium of high-quality, and this is a problem.
Contain a spot of coal dust in pending discharging gas, according to the equipment that uses, coal dust content is big sometimes, and in wet type ammonia desulfurizer, the coal dust in the discharging gas traps in the absorption liquid in the sulphur ammonium absorption process on above-mentioned absorption tower 12 usually.When the coal dust that is captured can not be removed in advance effectively, then sneak in the above-mentioned solid ammonium sulfate 28, and become the main cause that sulphur ammonium purity reduces.
In addition, in fuel, also contain trace heavy metals, and in above-mentioned embodiment in the past, in system, be concentrated, and sneak in the above-mentioned solid ammonium sulfate 28.And, in order to remove because of fouling remains in fouling in the system, the attended operation that must regularly clean etc.
Summary of the invention
The present invention drains into a part of parting liquid outside the system in view of above-mentioned actual conditions, and its amount is reduced, and simultaneously, improves the organic efficiency of sulphur ammonium, reduces the product cost of sulphur ammonium, prevents that further coal dust, heavy metal from sneaking into the sulphur ammonium, seeks the raising that sulphur ammonium goods are worth.
The flue gas desulfurization equipment that the present invention relates to, this device comprises, in the sulphur ammonium recovery line of extracting sulphur ammonium lysate out, from upstream side, the filter of separating solids composition, the seperator that makes crystallizing tank that the sulphur ammonium separates out, the sulphur ammonium that separates out is separated sequentially are set, the return line that the parting liquid that separated with this seperator is back to above-mentioned crystallizing tank also is set, and be that pH is adjusted upper reaches one side that liquid is supplied with above-mentioned filter, and the oronain concentration in the above-mentioned parting liquid is drained into a part of parting liquid outside the system with being lower than compound solubility; In addition, the invention still further relates to above-mentioned sulphur ammonium recovery line, extract the flue gas desulfurization equipment of sulphur ammonium lysate from the oxidation absorption tower of carrying out desulfurization, oxidation reaction out; In addition, the invention still further relates to mixer is set, the flue gas desulfurization equipment that the absorption liquid of storing in the oxidation absorption tower is stirred; And the invention still further relates to and make pH with ammoniacal liquor and adjust liquid, and supply to the flue gas desulfurization equipment in the sulphur ammonium lysate that reaches the pH value that to separate out heavy metal.
Owing to be under the concentration before oronain in being dissolved in parting liquid is separated out, discharge a part of parting liquid, so, in the sulphur ammonium that recovery obtains, do not sneak into the ammonia ammonium, and discharge rate is very little, and, can remove heavy metal, so, can use the liquid fertilizer of parting liquid as high concentration.In addition, the absorption liquid of seasoning in the oxidation absorption tower, stir with mixer, then the pH value of absorption liquid can reach stable, easily the supply of absorption liquid is controlled, and desulfurization performance is improved, and the coal dust that can prevent to discharge in the gas is deposited in the oxidation absorption tower.
Description of drawings
Fig. 1 is the structural representation that provides embodiment of the present invention.
Fig. 2 is the structural representation of exhausted smoke processing system that contains the coal-burning boiler device of flue gas desulfurization equipment.
Fig. 3 is the structural representation of flue gas desulfurization equipment in the past.
To the symbol description among the figure in down
7 desulfurizers
24 sulphur ammonium lysates
25 crystallizing tanks
26 steam
27 seperators
29 return lines
35 ammoniacal liquor supply lines
38 sulphur are by recovery line
39 filters
40 ammoniacal liquor supply take-off line
41 mixers
The specific embodiment
Below, the embodiment that invention will be further ex-plained with reference to the appended drawings.
In Fig. 1,, adopt same symbol with the same section shown in Fig. 3.In addition, the oxidation absorption tower shown in Fig. 1 31 is the integral body that absorption tower and chimney are formed.
The discharging conductance is gone into pipeline 32, supplementing water supply line 33, oxidation air supply line 34 and ammoniacal liquor supply line 35, is communicated with oxidation absorption tower 31, and goes into ventilation blower 36 is set in the pipeline 32 in above-mentioned discharging conductance.In addition, the mixer 41 that stirs absorption liquid 15 is set in above-mentioned oxidation absorption tower 31, simultaneously, the absorption liquid pipeloop 37 with absorption liquid circulating pump 16 is set, meet a branch, sulphur ammonium recovery line 38 is set from this absorption liquid pipeloop 37.
In the upper reaches of this sulphur ammonium recovery line 38 side, set gradually filter 39, crystallizing tank 25 and seperator 27,, be connected to upper reaches one side from the filter 39 of above-mentioned sulphur ammonium recovery line 38 with the branch line 40 of the ammoniacal liquor supply take-off line that branches out from ammoniacal liquor supply line 35.
In above-mentioned oxidation absorption tower 31, the pH detector is set, but not shown.And, in above-mentioned ammoniacal liquor supply line 35, ammoniacal liquor supply by-pass line 40, flow control valve is set respectively respectively, also not shown among the figure.
The following describes its effect.
Go into pipeline 32 from above-mentioned discharging conductance the discharging conductance is gone in the above-mentioned oxidation absorption tower 31, in this oxidation absorption tower 31, carry out gas-liquid with the absorption liquid 15 that circulates from above-mentioned absorption liquid pipeloop 37 and contact.Sulfur dioxide in the ammoniacal liquor of absorption liquid 15 and the discharging gas carries out desulphurization reaction, from discharging gas sulfur dioxide is absorbed to absorption liquid 15.
These absorption liquid 15 seasonings are in the bottom on above-mentioned oxidation absorption tower 31, circulate by above-mentioned absorption liquid pipeloop 37 again, the part of the absorption liquid 15 that circulates from this absorption liquid pipeloop 37, extract out from above-mentioned sulphur ammonium recovery line 38, in addition, absorption liquid 15 in above-mentioned oxidation absorption tower 31 is wanted level such to remain on, from make-up water supply line 33 supplementing water.In addition, the pH of above-mentioned absorption liquid 15 is detected by the pH detector, reaches institute's definite value with the pH that detects and controls like that from the ammonia vol of above-mentioned ammoniacal liquor supply line 35 supplies.
From above-mentioned oxidation air supply line 34 oxidation air is blown to above-mentioned absorption liquid 15, stir this absorption liquid 15 with above-mentioned mixer 41.Because oxidation air is blown to above-mentioned absorption liquid 15, make the further oxidation of the ammonium sulfite that in desulphurization reaction, generates, generate the sulphur ammonium.Also have, by in above-mentioned absorption liquid 15, being blown into oxidation air, the sometimes sulfuric acid that generates of the condition of looking local, yet, stir seasoning absorption liquid 15 with above-mentioned mixer 41, make even oxidation, can suppress the generation of sulfuric acid.Therefore, the pH of absorption liquid 15 is stable, is easy to control pH, promptly is easy to control the ammoniacal liquor supply from ammoniacal liquor supply line 35.Can remain on 5～6 to the pH of the absorption liquid 15 of above-mentioned oxidation absorption tower 31 bottom seasonings.
As mentioned above,, the change of pH can be suppressed, thereby the reduction and the instabilityization of desulfurization performance can be avoided because mixer 41 is set.
In addition, be contained in the coal dust in the discharging gas, contact and captured by gas-liquid, and be contained in the absorption liquid 15 of above-mentioned oxidation absorption tower 31 bottom seasonings with absorption liquid 15, owing to above-mentioned mixer 41 this absorption liquid 15 is stirred, can be prevented that it is deposited in the bottom on oxidation absorption tower 31.
The part (sulphur ammonium lysate 24) of the absorption liquid 15 of circulation from above-mentioned absorption liquid pipeloop 37, extract out by above-mentioned sulphur ammonium recovery line 38.From above-mentioned ammoniacal liquor supply by-pass line 40, ammoniacal liquor is supplied with in this sulphur ammonium recovery line 38, adjust the pH of the absorption liquid of extracting out 15.The pH of control through adjusting makes in the upstream of above-mentioned filter 39 to reach more than 7, for example, reaches 7～8.Because pH rises, and heavy metal is separated out.
The adjusted sulphur ammonium of pH lysate 24 is removed coal dust and above-mentioned heavy metal of separating out by above-mentioned filter 39.Sulphur ammonium lysate 24 seasonings behind removal coal dust and the heavy metal in crystallizing tank 25, in this crystallizing tank 25, are carried out heating evaporation with steam as thermal source, and the sulphur ammonium concentration of sulphur ammonium lysate 24 rises, and the sulphur ammonium is separated out.The sulphur ammonium 28 that separates out uses seperator 27 with its separation, outside the taking-up system.Parting liquid behind the separate sulfur ammonium 28 through return line 29, turns back in the above-mentioned crystallizing tank 25.
As mentioned above, in above-mentioned sulphur ammonium lysate 24, the oronain that generates in sweetening process has oligodynamical.With crystallizing tank 25 heating evaporations, and, return in the process of crystallizing tank 25 through above-mentioned return line 29 again, oronain concentration is concentrated gradually with seperator 27 separate sulfur ammoniums 28.
Provide the solubility of sulphur ammonium 28 and oronain below.
0 ℃ 20 ℃ 60 ℃ 100 ℃ of temperature
(NH
4)
2SO
4 41.35％ 42.85％ 46.6％ 50.4％
NH
4Cl 22.7％ 27.1％ 35.6％ 43.6％
The solubility of sulphur ammonium 28 and oronain is respectively 46.6% and 35.6% in the time of 60 ℃, both are in the compound solubility of dissolved state simultaneously, is not both solubility sums.Though sneaked into oronain, also to hold, be the sulphur ammonium 28 sulphur ammonium concentration of separating out down and the scope that oronain is not separated out as far as possible at the high area operation of oronain concentration, and makes the separation liquid measure the system of being evacuated to outside reach minimum.
For example, the compound solubility of supposing 60 ℃ of oronains is 15%, when the oronain solubility the sulphur ammonium lysate of extracting out from above-mentioned oxidation absorption tower 31 24 was 0.5%, even the compound solubility of oronain is concentrated into the parting liquid that reaches after 15%, it did not separate out oronain yet in above-mentioned return line 29.
Yet the parting liquid with above-mentioned seperator 27 separated when not surpassing the compound solubility of oronain, allows the part of this parting liquid drain into outside the system.The solubility of oronain of this moment for example, fixes in the example of Jie Shiing more than 5% below 10% in front.Therefore, as in the present embodiment the oronain concentration of the parting liquid of discharging being reached at 10% o'clock, then the discharge rate of parting liquid reaches 1/20 of from above-mentioned oxidation absorption tower 31 absorption liquids of extracting out 15, and this amount is few.And the amount of the discharging gas of handling with the desulfurizer in the present embodiment 7 is 50000m
3N/h, if when contained sulfur dioxide is 2000ppm, also can be according to contained hydrogen chloride amount, the discharge rate of above-mentioned parting liquid is reduced to is about 30l/h.Other exhaust gas desulfurization processing method, for example, the magnesium hydroxide method, under same condition, the lifting rate of discharge is 5000l/h, as seen, the amount of liquid that the desulfurizer 7 from the present embodiment is discharged is few significantly.
In addition, adopt the desulfurizer 7 of embodiment of the present invention, because used filter 39, coal dust contained in the sulphur ammonium lysate 24 in the above-mentioned sulphur ammonium recovery line 38 and heavy metal are removed, so, in above-mentioned return line 29, contain coal dust and heavy metal hardly, and contain the sulphur ammonium and the oronain of higher concentration.Same with the sulphur ammonium, oronain also is a fertilizer.The parting liquid of being discharged itself also is a fertilizer.Therefore, as with the fertilizer etc. of parting liquid as afforestation, then this flue gas desulfurization equipment can not have relief liquor fully.
Also having, in the above-described embodiment, is that the absorption tower that chimney becomes one is illustrated, yet, also can implement the present invention even the flue gas desulfurization equipment that chimney constitutes is set by other approach.In addition, above-mentioned sulphur ammonium recovery line 38 is come out from above-mentioned absorption liquid pipeloop 37 branches, yet, also can be arranged to directly from above-mentioned oxidation absorption tower 31 and extract absorption liquids 15 out.In addition, in order to regulate the pH of filter 39 upstreams, by above-mentioned ammoniacal liquor supply by-pass line 40 supply ammoniacal liquor, yet, also can supply ammoniacal liquor independently with ammoniacal liquor supply line 35.
The following describes effect of the present invention
As mentioned above, according to the present invention,, under the concentration before oronain in being dissolved in parting liquid is separated out a part of parting liquid is discharged because be, so, oronain can not be sneaked in the sulphur ammonium of recovery, and discharge rate is minimum, and, because carried out the further removal of heavy metal, so parting liquid can be used as liquid fertilizer and uses. In addition, because stir the absorption liquid of oxidation absorption tower seasoning with mixer, so, pH that can stable absorption liquid, easily carry out the supply control of absorption liquid, desulfurization performance can improve, and the coal dust in the discharging gas that can prevent from capturing in the absorption liquid precipitates in the oxidation absorption tower, available above-mentioned filter is removed coal dust again, in the sulphur ammonium that reclaims, do not sneak into coal dust, heavy metal and oronain, so brought into play excellent effect to obtaining high-quality sulphur ammonium.
Claims (4)
1. flue gas desulfurization equipment, it is characterized in that, this device comprises, in the sulphur ammonium recovery line of extracting sulphur ammonium lysate out, from upstream side, the filter of separating solids composition sequentially is set, separate out the seperator of the crystallizing tank of sulphur ammonium and the sulphur ammonium that separation is separated out, the return line that the parting liquid of separating with this seperator is turned back to above-mentioned crystallizing tank also is set, and pH is adjusted the sulphur ammonium lysate that liquid supplies to the upstream side of above-mentioned filter, make it reach the pH value that heavy metal is separated out, and the part of parting liquid is discharged to beyond the system, so that the oronain concentration in the above-mentioned parting liquid is lower than compound solubility.
2. the flue gas desulfurization equipment of record in the claim 1, wherein said sulphur ammonium recovery line is extracted sulphur ammonium lysate out from the oxidation absorption tower of carrying out desulfurization, oxidation reaction.
3. the flue gas desulfurization equipment of record in the claim 2 wherein is provided with the mixer that stirs the absorption liquid of storing in the oxidation absorption tower.
4. the flue gas desulfurization equipment of record in the claim 1, wherein to adjust liquid be ammoniacal liquor to pH.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11126270A JP2000317258A (en) | 1999-05-06 | 1999-05-06 | Flue gas desulfurization equipment |
| JP126270/1999 | 1999-05-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1273140A CN1273140A (en) | 2000-11-15 |
| CN1162206C true CN1162206C (en) | 2004-08-18 |
Family
ID=14931046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB00101918XA Expired - Lifetime CN1162206C (en) | 1999-05-06 | 2000-01-28 | Smoke discharging desulphurization device |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2000317258A (en) |
| CN (1) | CN1162206C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480571B (en) * | 2008-12-30 | 2014-01-01 | 上海华畅环保设备发展有限公司 | Method and apparatus for flue gas desulfurization and solid removal by wet-type ammonia process |
| KR100908409B1 (en) * | 2009-02-27 | 2009-07-20 | (주)랜드브릿지 | Equipment for manufacturing carbides using sludge |
| CN101991989B (en) * | 2010-10-21 | 2013-04-24 | 武汉钢铁(集团)公司 | Crystallization bypass filtering method and device in single tower |
| CN105223036B (en) * | 2015-09-28 | 2018-01-30 | 广东电网有限责任公司电力科学研究院 | MgO flue gas desulfurization performance on-site verification method and systems |
| CN111992017B (en) * | 2020-08-21 | 2023-03-10 | 中石化南京工程有限公司 | Combined ammonia desulphurization production method and device |
-
1999
- 1999-05-06 JP JP11126270A patent/JP2000317258A/en active Pending
-
2000
- 2000-01-28 CN CNB00101918XA patent/CN1162206C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000317258A (en) | 2000-11-21 |
| CN1273140A (en) | 2000-11-15 |
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Granted publication date: 20040818 |