CN100469418C - Fume desulfurizing process with enhancement limestone method - Google Patents
Fume desulfurizing process with enhancement limestone method Download PDFInfo
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- CN100469418C CN100469418C CNB2006100530766A CN200610053076A CN100469418C CN 100469418 C CN100469418 C CN 100469418C CN B2006100530766 A CNB2006100530766 A CN B2006100530766A CN 200610053076 A CN200610053076 A CN 200610053076A CN 100469418 C CN100469418 C CN 100469418C
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Abstract
The invention relates to a method for desulfurising smoke, especially a strengthen limestone smoke desulfurising method. Wherein, it comprises adding limestone and additive into reactor, to be mixed and reacted with water to generate adsorption slurry; inputting slurry into adsorption tower; the sulfur smoke enters into tower to react with slurry; the purified smoke is discharge outside the tower; the slurry with sulfur dioxide will be discharged at the bottom of tower to be recycled. The invention can improve desulfurising efficiency at 5-10% and improve the absorber utilization at 1-10%.
Description
Technical field
The present invention relates to a kind of flue gas desulfurization technique, particularly a kind of fume desulfurizing process with enhancement limestone method is mainly used in air contaminant treatment, Prevention Technique field.
Background technology
Flue gas desulfurization with a long history, just the someone has carried out the research of this respect before more than 100 years.At present, desulfur technology is concluded and can be divided into three major types: desulfurization before (1) burning, as coal washing, bacterial desulfurization; (2) desulfurization in the burning is as the solid sulphur of industrial shaping coal, in-furnace calcium spraying; (3) burning back desulfurization, i.e. flue gas desulfurization (FGD).The FGD method is the desulfur technology of in the world unique large-scale commercial applicationsization.The FGD technology mainly is the SO that utilizes in absorbent or the adsorbent removal flue gas
2, and make it be converted into the compound of more stable sulphur.The FGD technology is of a great variety, and still prevailing in current technology is wet type limestone/lime method.
Wet method limestone/lime flue gas desulfurization technique is to utilize lime with low cost and lime stone as the SO in the absorbent absorption flue gas
2, generate inferior sour calcium of half water or gypsum.This technology is once in that the seventies is big because of its investment, operating cost is high and problems such as burn into fouling, obstruction have influenced its application in thermal power plant.Through for many years practice and improvement, service behaviour and reliability greatly improve, and investment significantly reduces with operating cost, are flue gas desulfurization main method in the device introduced of present China.This method major advantage is: a. desulfuration efficiency height (during the device Ca/S=1 that has, desulfuration efficiency is greater than 95%); B. absorbent utilization rate height can be greater than 95%; C. operation rate height (can reach more than 95%).The enforcement period of the seventh five-year plan Chongqing Lopa Nationality semi-annular jade pendant power plant introduce the Mitsubishi heavy industry with supporting 2 cover wet type limestone/gypsum method flue gas desulfurization technique and the equipment of 2 * 360MW unit, take the lead in having built up large power plant boiler flue gas desulfurization demonstration project, and the commercial running of formal input in 1992 and 1993, system's desulfurization degree reaches more than 95%, and by-produced gypsum purity is higher than 90%.
Also need greatly, in addition the sulphite that reaction in the sweetening process generates is carried out the reliability service that oxidation control (forced oxidation or inhibition oxidation) guarantees system but existing wet method limestone/lime flue gas desulfurization technique major defect is investment, cause operating cost higher.
Summary of the invention
The invention provides a kind of raising sorbent utilization, reduce desulphurization cost, need not to carry out the fume desulfurizing process with enhancement limestone method that oxidation control can be avoided system's fouling simultaneously.
A kind of fume desulfurizing process with enhancement limestone method is imported digestion reactor respectively with lime stone and additive, mixes and generate with the water reaction at digestion reactor sodalime stone and additive to absorb slurries; To absorb slurries input absorption tower, and after sulfur-containing smoke gas enters the absorption tower and absorbs slurry reaction, purify flue gas and discharge the absorption tower; The absorption slurries that absorbed sulfur dioxide recycle or go post processing after the discharge of bottom, absorption tower.
Last handling process comprises: enter into hydrocyclone after the absorption slurries that will absorb sulfur dioxide are discharged from the bottom, absorption tower and carry out Separation of Solid and Liquid, the top of cyclone flow back in the absorption tower, or go digestion reactor to apply mechanically, the underflow of cyclone enters into vacuum band-type filter machine and further dewaters, make the low desulfurization slag of moisture content and efflux, filtrate discharge or go digestion reactor to apply mechanically.
Additive is organic acid and/or inorganic additive, and organic acid is: at least a in adipic acid, citric acid, humic acid, benzoic acid, the acetate; Inorganic additive is: at least a in magnesia, sodium sulphate, the sodium nitrate.
The absorption tower is packed tower, sieve-plate tower, rotating stream tray scrubber or venturi.Be provided with the side direction agitating device in the bottom on absorption tower, prevent to absorb the precipitation of slurries.
The sulfur removal technology condition: advancing tower absorption slurry pH value is 5.0-9.0, and liquid-gas ratio is 2.0-20.0L/m
3, inorganic additive concentration 0-100000mg/L, organic acid 0-3000mg/L, inorganic additive and organic acid concentration are not 0mg/L simultaneously.Calcium ion concentration 600-2000mg/L absorbs slurries mass percent concentration 1-35%, can realize that desulfuration efficiency is greater than 95%.
Technical process of the present invention is:
Absorbent lime stone and additive enter digestion reactor by feed arrangement and metering device separately.At digestion reactor sodalime stone and additive and water reaction generation absorption slurries (additive is example with magnesia).
Absorption slurries after digestion reaction is intact enter the absorption tower by absorbing the slurries delivery pump, and sulfur-containing smoke gas enters the absorption tower, carry out desulphurization reaction with the absorption slurries in inside, absorption tower:
If it is as follows that additive is that organic acid then reacts:
Sulfur dioxide+water=acid (H
+)+inferior sulfate radical
Organic buffer anion+acid (H
+)=organic acid
In desulfurizing tower, organic acid and lime stone reaction obtain regeneration:
Organic acid+inferior sulfate radical+calcium carbonate=organic buffer anion+calcium sulfite+carbon dioxide
Purify flue gas and discharge, after the absorption slurries that absorbed sulfur dioxide arrive the bottom, absorption tower, recycle, perhaps go post processing by main circulation pump from the top, absorption tower.
When reaching, the absorption slurries just need post processing when finite concentration can not recycle use.
A part of slurries are discharged by the desulfurization slag delivery pump in the bottom, absorption tower, enter through hydrocyclone, after separating in cyclone, the top of cyclone flow back in the absorption tower, or going digestion reactor water jacket usefulness as a supplement, underflow further dewaters through vacuum band-type filter machine and obtains desulfurization slag.
Fume desulfurizing process with enhancement limestone method of the present invention adopts lime stone and certain proportion of additive desulfurization together, improve the pH buffer capacity of desulfurization absorption slurries and ion concentration of inferior sulfate radical wherein, effectively reduce calcium ion concentration, avoid the fouling of calcium sulfite and calcium sulfate, improve the utilization rate of lime stone simultaneously, reduce desulphurization cost.Compare with traditional limestone-based process, can improve the about 5-10% of desulfuration efficiency under identical liquid-gas ratio condition, the absorbent utilization rate improves 1-10%.
Description of drawings
Fig. 1 is an enhancement limestone method process chart, wherein:
1, absorption tower 2, sulfur-containing smoke gas 3, technology flushing water
4, purify flue gas 5, lime stone storehouse 6, additive bin
7, conveying worm 8, digestion reactor 9, absorption slurries delivery pump
10, cyclone 11, vacuum band-type filter machine 12, filtrate pump
13, filtrate receiver 14, desulfurization slag delivery pump 15, main circulation pump
16, technology supplementing water 17, efflux part filtrate 18, lime stone grinder
The specific embodiment
Embodiment 1
Referring to Fig. 1, absorbent agstone and additive are stored in respectively in lime stone storehouse 5, the additive bin 6, and conveying worm 7 and metering device by separately enter digestion reactor 8.If limestone block, enter lime stone storehouse 5 after then wearing into powder by lime stone grinder 18.If liquid additive then can be directly by fluid-carrying lines with additive delivery in digestion reactor 8.
Generate and absorb slurries in digestion reactor 8 sodalime stones and additive and water (can be technology supplementing water 16 or from the filtrate or the top of cyclone 10 stream of filtrate receiver 13) reaction.
Absorption slurries after digestion reaction is intact are transported on the output pipe of main circulation pump 15 by absorbing slurries delivery pump 9, perhaps directly enter absorption tower 1.
Sulfur-containing smoke gas 2 enters absorption tower 1, with absorb slurries and react 1 inside on the absorption tower, purify flue gas 4 and discharge 1 top, after the absorption slurries that absorbed sulfur dioxide arrive 1 bottom, absorption tower from the absorption tower, enter main circulation pump 15 by export pipeline and recycle, perhaps go post processing.Be provided with the side direction agitating device in the bottom on absorption tower, prevent to absorb the slurries precipitation.
Slurries after the absorption are when reaching certain concentration and need post processing later on, enter into hydrocyclone 10 by desulfurization slag delivery pump 14 and carry out Separation of Solid and Liquid, the underflow of cyclone 10 enters into vacuum band-type filter machine 11 and further dewaters, and makes the low desulfurization slag of moisture content and effluxes.The top of cyclone 10 flow back in the absorption tower 1, also can go digestion reactor 8 water jacket usefulness as a supplement.The filtrate of vacuum band-type filter machine 11 is transported in the digestion reactor 8 by filtrate pump 12 and applies mechanically, and absorbs then to efflux part filtrate 17 by filtrate pump 12 after ion concentration in the slurries is accumulated to a certain degree.
Technology flushing water 3 can clean equipment when needed.
Carry out the supporting flue gas desulfurization technique of 410t/h boiler according to above-mentioned technical process, boiler smoke import SO
2Concentration is 2037mg/m
3, flue-gas temperature is 155 ℃, and advancing tower pH is 7.0, and liquid-gas ratio is 3.0L/m
3, magnesium ion concentration is 100000mg/L, and calcium ion concentration is 668mg/L, and absorbing the concentration of slurry mass ratio is 18.0%, and desulfuration efficiency reaches 95.0%.
Embodiment 2
Carry out the supporting flue gas desulfurization of 220t/h boiler according to embodiment 1 described technical process.Boiler smoke import SO
2Concentration is 9690mg/m
3, temperature is 160 ℃, and advancing tower pH is 5.0, and liquid-gas ratio is 20.0L/m
3, the sodium sulphate ion concentration is 2852mg/L, and calcium ion concentration is 620mg/L, and absorbing the concentration of slurry mass ratio is 11.7%, and desulfuration efficiency reaches 97.0%.
Embodiment 3
Carry out the supporting flue gas desulfurization technique of 130t/h boiler according to embodiment 1 described technical process, boiler smoke import SO
2Concentration is 2050mg/m
3, temperature is 155 ℃, and advancing tower pH is 6.5, and liquid-gas ratio is 5.0L/m
3, sodium nitrate concentration is 5096mg/L, and calcium ion concentration is 600mg/L, and absorbing the concentration of slurry mass ratio is 13.0%, and desulfuration efficiency is 96.1%.
Embodiment 4
Carry out the supporting flue gas desulfurization of 170t/h boiler according to embodiment 1 described technical process.Boiler smoke import SO
2Concentration is 1800mg/m
3, temperature is 152 ℃, and advancing tower pH is 6.0, and liquid-gas ratio is 4.0L/m
3, concentration of adipic acid is 3000mg/L, and calcium ion concentration is 600mg/L, and absorbing the concentration of slurry mass ratio is 11.0%, and desulfuration efficiency is 95.8%.
Embodiment 5
Carry out the supporting flue gas desulfurization of 75t/h boiler according to embodiment 1 described technical process.Boiler smoke import SO
2Concentration is 2060mg/m
3, temperature is 155 ℃, and advancing tower pH is 6.0, and liquid-gas ratio is 5.0L/m
3, citric acid concentration is 1960mg/L, and calcium ion concentration is 940mg/L, and absorbing the concentration of slurry mass ratio is 12.0%, and desulfuration efficiency is 96.0%.
Embodiment 6
Carry out the supporting flue gas desulfurization of 170t/h boiler according to embodiment 1 described technical process.Boiler smoke import SO
2Concentration is 1050mg/m
3, temperature is 160 ℃, and advancing tower pH is 6.5, and liquid-gas ratio is 2.0L/m
3, humic acid concentration is 100mg/L, and calcium ion concentration is 2000mg/L, and absorbing the concentration of slurry mass ratio is 15.0%, and desulfuration efficiency is 95.1%.
Embodiment 7
Carry out the supporting flue gas desulfurization of 220t/h boiler according to embodiment 1 described technical process.Boiler smoke import SO
2Concentration is 2590mg/m
3, temperature is 165 ℃, and advancing tower pH is 7.0, and liquid-gas ratio is 5.0L/m
3, magnesium ion concentration is 4203mg/L, and concentration of adipic acid is 500mg/L, and calcium ion concentration is 600mg/L, and absorbing the concentration of slurry mass ratio is 13.0%, desulfuration efficiency is 97.0%.
Embodiment 8
Carry out the supporting flue gas desulfurization of 170t/h boiler according to embodiment 1 described technical process.Boiler smoke import SO
2Concentration is 1700mg/m
3, temperature is 165 ℃, and advancing tower pH is 5.8, and liquid-gas ratio is 5.0L/m
3, magnesium ion concentration is 4416mg/L, and citric acid concentration is 300mg/L, and calcium ion concentration is 560mg/L, and absorbing the concentration of slurry mass ratio is 12.6%, desulfuration efficiency is 98.4%.
Embodiment 9
Carry out the supporting flue gas desulfurization of 130t/h boiler according to embodiment 1 described technical process.Boiler smoke import SO
2Concentration is 9900mg/m
3, temperature is 168 ℃, and advancing tower pH is 9.0, and liquid-gas ratio is 20.0L/m
3, magnesium ion concentration is 7332mg/L, and humic acid concentration is 1000mg/L, and calcium ion concentration is 600mg/L, and absorbing the concentration of slurry mass ratio is 17.0%, desulfuration efficiency is 98.8%.
Embodiment 10
Carry out the supporting flue gas desulfurization of 410t/h boiler according to embodiment 1 described technical process.Boiler smoke import SO
2Concentration is 1900mg/m
3, temperature is 156 ℃, and advancing tower pH is 7.0, and liquid-gas ratio is 4.0L/m
3, sodium sulfate concentration is 2368mg/L, and concentration of adipic acid is 100mg/L, and calcium ion concentration is 1120mg/L, and absorbing the concentration of slurry mass ratio is 13.0%, desulfuration efficiency is 96.0%.
Claims (4)
1, a kind of fume desulfurizing process with enhancement limestone method comprises: lime stone and additive are imported digestion reactor respectively, mix and generate with the water reaction at digestion reactor sodalime stone and additive and absorb slurries; To absorb slurries input absorption tower, and after sulfur-containing smoke gas enters the absorption tower and absorbs slurry reaction, purify flue gas and discharge the absorption tower; The absorption slurries that absorbed sulfur dioxide recycle or go post processing after the discharge of bottom, absorption tower;
Described additive is the humic acid of concentration 1000mg/L and the magnesium ion of 7332mg/L;
PH value when described absorption slurries enter the absorption tower is 9.0.
2, fume desulfurizing process with enhancement limestone method according to claim 1, it is characterized in that: described post processing comprises: enter into hydrocyclone after the absorption slurries that will absorb sulfur dioxide are discharged from the bottom, absorption tower and carry out Separation of Solid and Liquid, the top of cyclone flow back in the absorption tower, or go digestion reactor to apply mechanically, the underflow of cyclone enters into vacuum band-type filter machine and further dewaters, make the low desulfurization slag of moisture content and efflux, filtrate discharge or go digestion reactor to apply mechanically.
3, fume desulfurizing process with enhancement limestone method according to claim 1 is characterized in that: liquid-gas ratio is 20.0L/m when carrying out absorption reaction in the absorption tower
3
4, fume desulfurizing process with enhancement limestone method according to claim 1 is characterized in that: calcium ion concentration is 600mg/L when carrying out absorption reaction in the absorption tower.
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| CNB2006100530766A CN100469418C (en) | 2006-08-18 | 2006-08-18 | Fume desulfurizing process with enhancement limestone method |
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| CNB2006100530766A CN100469418C (en) | 2006-08-18 | 2006-08-18 | Fume desulfurizing process with enhancement limestone method |
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| CN100469418C true CN100469418C (en) | 2009-03-18 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101342460B (en) * | 2008-08-20 | 2011-08-17 | 浙江天蓝环保技术有限公司 | Automatically controlled desulphurizing agent slurry formulating device |
| CN102000481B (en) * | 2009-08-31 | 2012-10-10 | 宝山钢铁股份有限公司 | Method for treating desulfurization ash |
| CN101947410A (en) * | 2010-09-28 | 2011-01-19 | 浙江天达环保股份有限公司 | Active activator of limestone powder |
| CN102019138B (en) * | 2010-11-18 | 2013-02-13 | 华北电力大学（保定） | Multifunctional composite additive for wet-method flue gas desulfuration process and using method thereof |
| CN102000489A (en) * | 2010-11-24 | 2011-04-06 | 东北电力科学研究院有限公司 | Wet desulfurizer for thermal power plant and desulfurization method thereof |
| CN102183518A (en) * | 2011-01-26 | 2011-09-14 | 中节能六合天融环保科技有限公司 | Method for quickly measuring sulfate radical content in magnesium method desulfurization process |
| CN102485323A (en) * | 2011-04-15 | 2012-06-06 | 安徽理工大学 | Rapid calcium desulphurization method for flue gas |
| CN109126409A (en) * | 2018-10-30 | 2019-01-04 | 中冶焦耐(大连)工程技术有限公司 | It is a kind of that desulfurization and decarburization technique being carried out to biogas with causticization liquid |
| CN111013345A (en) * | 2019-12-05 | 2020-04-17 | 盛尼克能源环保技术(重庆)有限公司 | Wet flue gas desulfurization method by adding magnesium limestone |
| CN114682161A (en) * | 2020-12-26 | 2022-07-01 | 黄华丽 | Solid-liquid different-weight mixed slurry material storage tank and application thereof |
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Address after: Hangzhou City, Zhejiang Province, Xihu District Wensanlu Road 310012 building room 1019, No. 369 digital Co-patentee after: Wu Zhongbiao Patentee after: ZHEJIANG TIANLAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: Hangzhou City, Zhejiang Province, Xihu District Wensanlu Road 310012 building room 1019, No. 369 digital Co-patentee before: Wu Zhongbiao Patentee before: Zhejiang Tianlan Desulphurization & Dust-Removal Co.,Ltd. |
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Address after: Hangzhou City, Zhejiang province Xiaoshan District 311202 North Street Xingyi Village Patentee after: ZHEJIANG TIANLAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: Hangzhou City, Zhejiang province Xiaoshan District 311202 North Street Xingyi Village Patentee before: ZHEJIANG TIANLAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |