CN102188897B - Wet flue gas desulfurization and denitrification combined method - Google Patents
Wet flue gas desulfurization and denitrification combined method Download PDFInfo
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- CN102188897B CN102188897B CN2011101204801A CN201110120480A CN102188897B CN 102188897 B CN102188897 B CN 102188897B CN 2011101204801 A CN2011101204801 A CN 2011101204801A CN 201110120480 A CN201110120480 A CN 201110120480A CN 102188897 B CN102188897 B CN 102188897B
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- 239000003546 flue gas Substances 0.000 title claims abstract description 46
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 27
- 230000023556 desulfurization Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 235000019738 Limestone Nutrition 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000006028 limestone Substances 0.000 claims abstract description 13
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 5
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 7
- 239000004568 cement Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 15
- 238000005507 spraying Methods 0.000 abstract description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005708 Sodium hypochlorite Substances 0.000 abstract 1
- 229910052925 anhydrite Inorganic materials 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract 1
- 235000010261 calcium sulphite Nutrition 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000009897 systematic effect Effects 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to a wet flue gas desulfurization and denitrification combined method. In an absorption tower, a desulfurizing agent, namely lime stone slurry reacts with SO2 in flue gas in a spraying mode, oxidizing air is input to oxidize CaSO3 in tower bottom slurry into CaSO4, and a part of tower bottom slurry is extracted and returns to the tower to be sprayed; a denitrification oxidizing agent, namely potassium permanganate, hydrogen peroxide or sodium hypochlorite and an inhibitor, namely cerium oxide or vanadium pentoxide are introduced into the original flue and introduced into the absorption tower with the flue gas, and a denitrification reducing agent, namely urea or diammonium hydrogen phosphate and a stabilizer, namely ethylenediamine or ammonium phosphate are added into the absorption tower in the spraying mode; and the weight ratio of the denitrification oxidizing agent to the inhibitor is 1:(0.01-0.1), and the weight ratio of the denitrification reducing agent to the stabilizer is 1:(0.0001-0.001). By the method, the problem that denitrification and desulfurization restricts each other is well solved, the flue gas is efficiently subjected to denitrification and desulfurization in the same device simultaneously to reach the discharge standard, and sulfur dioxide and nitrogen oxide are prevented from polluting an environment.
Description
Technical field
Patent of the present invention relates to a kind of wet flue gas combined desulfurization denitrogenation method, belongs to the purifying coal-fired flue gas field.
Background technology
China is that maximum in the world fire coal consumes state, and wherein fire coal is consumed the sulfur dioxide (SO that coal-fired flue-gas discharges more than 60% by thermal power station and big-and-middle-sized coal-burning boiler
2), nitrogen oxide (NOx) is one of primary pollution source of China's atmosphere, wherein power plant and Industrial Boiler stove account for about 70% of total release.In recent years, along with the fast development of Chinese national economy, the exhaust emission of flue gas is sustainable growth trend.Therefore, the SO of control coal-fired flue-gas
2And NO
xDischarging be the important step of environment protection.
Coal-fired SO
2, NO
XPollutant control is the Focal point and difficult point that China's atmosphere quality is improved.Aspect pollution that caused by coal burning thing control technology, the control of the sulfur dioxide overwhelming majority adopts wet method limestone-gypsum sulfur removal technology.From Eleventh Five-Year Plan, the newly-built fired power generating unit of China has all been built wet desulphurization device.Along with the enforcement of atmosphere pollutants emission standards GB13223-2003, do not build in the past the unit of desulfurizer, except closing down, substantially all added desulfurizer; In the desulfurizer of building, 85% adopts wet method limestone/gypsum sulfur removal technology.Along with reaching its maturity of Wet Flue Gas Desulfurization Technique, cost and the operating cost of wet desulphurization device significantly descend.But the control of nitrogen oxide is at present domestic or take imported technology as main, the overwhelming majority adopts Selective Catalytic Reduction (SCR) techniques.The initial cost of this process system is large, and operating cost is high.
For investment cost and the operating cost of the system of saving, the task of top priority is to develop the flue gas combined technology that removes with denitrification functions on the wet desulphurization basis.
Summary of the invention
The purpose of patent of the present invention provides a kind of wet flue gas combined desulfurization denitrogenation method, is implemented in and realizes simultaneously desulfurization and denitrogenation in the same device, improves desulfuration efficiency, reduces the denitrogenation cost.
Wet flue gas combined desulfurization denitrogenation method is as follows: in the absorption tower, use the desulfurizing agent lime stone slurry with the mode of spray and the SO in the flue gas
2Reaction, reaction product CaSO
3At the bottom of droping to tower with slurries, input oxidation air at the bottom of the tower is with the CaSO in the slurries that drop at the bottom of the tower
3Be oxidized to CaSO
4, extract a part of tower prime cement liquid out by slurry circulating pump simultaneously and return the spray that participates in the tower flue gas; It is characterized in that denitrogenation oxidant and inhibitor are passed in the former flue, make it enter the absorption tower with flue gas, the mode with spray adds denitrogenation reducing agent and stabilizing agent in the absorption tower simultaneously; Described denitrogenation oxidant is potassium permanganate, hydrogen peroxide or clorox, and inhibitor is cerium oxide or vanadic anhydride; Described denitrogenation reducing agent is urea or diammonium hydrogen phosphate, and stabilizing agent is ethylenediamine or ammonium phosphate;
The weight ratio of denitrogenation oxidant and inhibitor is 1: 0.01～0.1,
The weight ratio of denitrogenation reducing agent and stabilizing agent is 1: 0.0001～0.001.
Described denitrogenation oxidant potassium permanganate or clorox with add 1～10 times of weight water stirring and dissolving after inhibitor mixes in proportion and become solution, described denitrogenation reducing agent with add 1～15 times of weight water after stabilizing agent mixes in proportion and stir into solution.
Described denitrogenation reducing agent and stabilizing agent are added in the front pipeline of entrance of tower prime cement liquid circulating pump, send in the lump in the absorption tower with the tower prime cement liquid of extracting out, participate in the spray to flue gas.
The present invention is directed to NO and be slightly soluble in water, do not give birth to reaction with steeping in water for reconstitution and the difficult characteristics that remove added denitrogenation oxidant potassium permanganate, clorox or hydrogen peroxide before flue gas enters tower, the NO in the flue gas is oxidized to can be water-soluble or the NO of alkaline solution
2(suc as formula 1-1) makes it to be easy to remove.But because the denitrogenation oxidant has very strong oxidability, in oxidation NO, also may be with the SO in the flue gas
2Be oxidized to SO
3(seeing formula 1-2); And SO
3In flue gas, form easily " aerosol ", thereby can cause the reduction of desulfuration efficiency.The present invention adds in the denitrogenation oxidant and presses down agent cerium oxide or vanadic anhydride, can suppress SO
2Be oxidized to SO
3Reaction, namely inhibitory reaction formula 1-2 occurs, thereby avoids forming " aerosol " and affect desulfurized effect in the absorption tower.Then, NO
2Together enter the absorption tower with flue gas, enter tower flue gas and in uphill process, be desulfurized the absorbent lime stone slurry and from the spray of the loop slurry at the bottom of the tower, make SO wherein
2Generate CaSO with the limewash reaction
3, CaSO
3Drop to oxidation pond at the bottom of the tower, oxidized air oxygen changes into CaSO
4Slurries (gypsum slurries).Meanwhile, NO
2Generate HNO at Ta Nei and water reaction
2(suc as formula 1-4).By slurry circulating pump and lime stone slurry one flue gas spray in the tower in the same way, no matter the denitrogenation reducing agent is urea, diammonium hydrogen phosphate or diammonium hydrogen phosphate to this method with denitrogenation reducing agent and stabilizing agent, all take amino as main, and when it sprays in the tower, can be with HNO
2Reduction generates the N of environmental sound
2(seeing formula 1-5).Yet the denitrogenation reducing agent is alkaline solution, it can and SO
2React and generation ammonium salt (formula 1-6), this reaction can consume denitrogenation reducing agent, and the concentration of denitrogenation reducing agent is sharply descended, and affects denitrification effect.The present invention adopts the scheme that adds stabilizing agent ethylenediamine or ammonium phosphate in the denitrogenation reducing agent, and inhibitory reaction formula 1-6 occurs, and stablizes the concentration of reducing agent, under the prerequisite that does not affect desulfuration efficiency, can stablize the reducing power of nitrogen oxide, reduces the consumption of reducing agent.
2NO
2+H
2O→HNO
2+HNO
3 (1-3)
HNO
3→2HNO
2+O
2 (1-4)
In sum, the present invention has solved the problem that denitrogenation and the two existence of desulfurization condition each other well, need not to establish in addition special-purpose nitrogen rejection facility, can make flue gas in denitrogenation, still have higher desulfuration efficiency at original wet desulphurization device, remove expeditiously simultaneously nitrogen and sulphur, increase less cost, can realize the combined desulfurization denitrogenation, greatly reduce the investment of system; In addition, the present invention is combined with the SCR denitride technology, can reduce the design capacity of SCR, reduces SR, has reduced simultaneously catalyst amount, reduces the SCR systematic running cost and uses.
Description of drawings
Fig. 1 is wet flue gas combined desulfurization nitrogen rejection facility schematic diagram.
Among the figure, the former flue gas of 1-, the former flue of 2-, 3-expansion joint, the 4-absorption tower, 5-nozzle, 6-spraying layer, 7-porous plate ring, the 8-demister, the clean flue gas of 9-, 10-agitator, 11-oxidation air pipe, the 12-slurry circulating pump, 13-oxidation trough, 14-desulfurization absorbent storing and supplying device, 15-finished product lime stone slurry, the 16-accessory substance, 17-accessory substance treating apparatus, 18-denitrogenation oxidant stores supply system, 19-finished product denitrogenation oxidant, 20-denitrogenation reducing agent storing and supplying device, 21-finished product denitrogenation reducing agent.
The specific embodiment
Implementation process below in conjunction with description of drawings wet flue gas combined desulfurization of the present invention denitrogenation method.
Take potassium permanganate, clorox as the denitrogenation oxidant with inhibitor cerium oxide or vanadic anhydride by weight 1: mix (0.01～0.1), add 1～10 times of weight water stirring and dissolving and get finished product denitrogenation oxidant, or be the denitrogenation oxidant with hydrogen peroxide, directly with inhibitor cerium oxide or vanadic anhydride by weight 1: (0.01～0.1) is mixed, is dissolved, and gets finished product denitrogenation oxidant 19.
Take urea, diammonium hydrogen phosphate as the denitrogenation reducing agent, take ethylenediamine or ammonium phosphate as stabilizing agent, the two is by weight 1: mix (0.0001～0.001), adds 1～15 times of weight water and stir into solution and get finished product denitrogenation reducing agent 21.
Take lime stone as desulfurization absorbent, agstone and industry water are mixed product lime stone slurry 15.
As shown in Figure 1, former flue 2 is connected by the smoke inlet of expansion joint 3 with absorption tower 4.Be provided with spraying layer 6, porous plate ring 7 in the absorption tower 4, difference nozzle 5 on each spraying layer 6 (in this example, nozzle 5 oppositely arranges between adjacent spraying layer each other), cat head is provided with demister 8, and tower bottom is oxidation trough 13.Be connected with the slurries circulation pipe between oxidation trough 13 and the spraying layer 6, each circulation pipe is equipped with slurry circulating pump 12.Be provided with oxidation air pipe 11 and agitator 10 in the oxidation trough 13.
With the former flue 2 of finished product denitrogenation oxidant 19 inputs, the part NO in the former flue gas 1 is oxidized to NO
2, simultaneously, inhibitor wherein suppresses the SO in the flue gas
2Be oxidized to SO
3Contain subsequently NO, NO
2, SO
2Flue gas enter absorption tower 4 through expansion joint 3, and constantly rise to the cat head direction.
Desulfurization absorbent lime stone slurry 15 and finished product reducing agent 21 are by slurry circulating pump 12 input spraying layers 6, and to tower 4 interior sprays, slurries contact SO with the flue gas of rising by nozzle 5
2Generate CaSO with the lime stone reaction
3Slurries, CaSO
3The unreacted lime stone slurry of slurries and part together gravity drops to oxidation trough 13 at the bottom of the tower, under agitator 10 stirs, and CaSO
3The air oxidation that oxidized air hose 11 passes into is CaSO
4(gypsum), gypsum slurries 16, enter byproduct for treatment device 17 after, obtain by-produced gypsum.On the other hand, oxidation trough 13 interior part slurries are extracted out by slurry circulating pump 12 and are converged with desulfurization absorbent lime stone slurry 15 and the finished product reducing agent 21 inputted, return the spray that spraying layer 6 participates in the rising flue gas in the tower, NO by circulation line
2Generating HNO with the water reaction
2, the denitrogenation reducing agent is with HNO
2Reduction generates the N of environmental sound
2, it can with the flue gas 9 after purifying through demister 8, enter atmosphere from flue outlet through chimney; Stabilizer wherein prevents denitrogenation reducing agent and SO
2Reaction generates ammonium salt, plays the effect of stablizing reductant concentration.
The wet flue gas combined desulfurization nitrogen rejection facility of implementing the inventive method moves in the 3 * 25MW of Jiangsu power plant for self-supply unit, and relevant parameters is listed in table 1.
Table 1
The wet flue gas combined desulfurization nitrogen rejection facility of implementing the inventive method moves in the state's electricity northwest 2 * 300MW of genco unit, and relevant parameters is listed in table 2.
Table 2
Claims (3)
1. wet flue gas combined desulfurization denitrogenation method, in the absorption tower, the desulfurizing agent lime stone slurry is with the mode of spray and the SO in the flue gas
2Reaction, input oxidation air at the bottom of the tower is with the CaSO in the slurries that drop at the bottom of the tower
3Be oxidized to CaSO
4, extract a part of tower prime cement liquid out by slurry circulating pump simultaneously and return the spray that participates in the tower flue gas; It is characterized in that denitrogenation oxidant and inhibitor are passed in the former flue, make it enter the absorption tower with flue gas, the mode with spray adds denitrogenation reducing agent and stabilizing agent in the absorption tower simultaneously; Described denitrogenation oxidant is potassium permanganate, hydrogen peroxide or clorox, and inhibitor is cerium oxide or vanadic anhydride; Described denitrogenation reducing agent is urea or diammonium hydrogen phosphate, and stabilizing agent is second two ammoniums or ammonium phosphate; Wherein:
The weight ratio of denitrogenation oxidant and inhibitor is 1: 0.01～0.1,
The weight ratio of denitrogenation reducing agent and stabilizing agent is 1: 0.0001～0.001.
2. wet flue gas combined desulfurization denitrogenation method according to claim 1, add 1～10 times of weight water stirring and dissolving after it is characterized in that described denitrogenation oxidant potassium permanganate or clorox and inhibitor mixing in proportion and become solution, described denitrogenation reducing agent with add 1～15 times of weight water stirring and dissolving after stabilizing agent mixes in proportion and become solution.
3. wet flue gas combined desulfurization denitrogenation method according to claim 1 and 2, it is characterized in that described denitrogenation reducing agent and stabilizing agent are added in the front pipeline of entrance of tower prime cement liquid circulating pump, send in the lump in the absorption tower with the tower prime cement liquid of extracting out, participate in the spray to flue gas.
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| CN102728215B (en) * | 2012-07-25 | 2015-02-04 | 上海宇欢化工科技有限公司 | Composition and method for removing nitrogen oxides in desulfurizing tower |
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| CN112844028B (en) * | 2021-02-26 | 2022-09-20 | 陕西中科启明环保科技有限公司 | Industrial kiln flue gas denitration agent and preparation method and application thereof |
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