CN101780368A - Low energy consumption flue gas wet desulphurization process - Google Patents

Low energy consumption flue gas wet desulphurization process Download PDF

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Publication number
CN101780368A
CN101780368A CN201010133230A CN201010133230A CN101780368A CN 101780368 A CN101780368 A CN 101780368A CN 201010133230 A CN201010133230 A CN 201010133230A CN 201010133230 A CN201010133230 A CN 201010133230A CN 101780368 A CN101780368 A CN 101780368A
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flue gas
energy consumption
desulphurization
low energy
wet desulphurization
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张蕊
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张蕊
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Abstract

The invention provides a low energy consumption flue gas wet desulphurization process. A desulphurizing tower is adopted as a sulphur dioxide absorber, flue gas after primary dust removal reacted with cleaning solution containing alkaline absorbing agent in reverse washing cycle to remove sulphur dioxide in the flue gas, meanwhile part of circulating water (determined according to desulphurization product amount) is extracted and enters into a flue gas crystallizing evaporator to be evaporated before the desulphurization tower, and temperature of the flue gas is reduced while desulphurization product is separated out by crystallization. The process of the invention utilizes flue gas crystallizing evaporator to evaporate desulphurization product, thus substituting desulphurization product dehydration equipment; flue gas waste heat is effective utilized and substitutes energy consumption in dehydration of desulphurization product, water consumption in dehydration process is reduced, thus being applicable to flue gas sulphur dioxide removal by adopting calcium series or ammonia series (liquid ammonia, ammonia water, ammonium acid carbonate) desulphurizing agent; and operation energy consumption is low, thus having good economic benefit and social benefit.

Description

A kind of low energy consumption flue gas wet desulphurization process
Technical field
The present invention relates to flue gas desulfurization technique, relate in particular to a kind of industry spot and effective flue gas wet desulphurization process of investing, effectively reducing operation energy consumption that reduces of can be applicable to.
Background technology
China is the energy resource structure country based on fire coal, a large amount of fossil fuels are utilized to live for heating and industrial production, continuous growth along with consumption of coal, a large amount of carbon dioxide and sulfur dioxide have been discharged, Atmospheric Carbon Dioxide causes greenhouse effects, climate is warmed, constitute long-term hazards; Sulfur dioxide accumulation then formation acid rain, harm vegeto-animal normal existence in the face of land and life.The flue gas desulfurization technique of seeking the low operation energy consumption of a kind of low investment is people's long-term aim, meets people and pursues the low-carbon (LC) an aim in life.
Calcium is desulfurization, be that the limestone/lime-gypsum wet method is the most ripe, the most widely used flue gas desulfurization technique in the world today, it adopts lime stone or lime to make desulfurization absorbent, lime stone mixes with water to stir through the pulverizing and jevigating powdering makes absorbent slurry (when adopting lime to be absorbent, pulverized limestone adds the water stirring and makes the absorbent slurry after digestion process).In desulfurizing tower, absorbent slurry contacts mixing, the SO in the flue gas with flue gas 2Carry out chemical reaction with calcium carbonate in the slurries and the oxidation air that blasts, final reacting product is a gypsum.Be retracted to hydrocyclone with the calcium plaster liquid pump when reaching finite concentration (more than 15%) in the loop slurry and be concentrated to more than 50%, continuing to dewater to vacuum belt machine or filter press again is lower than 10% to water content and reclaims.Be respectively about 2,500,000 tons and 3,500,000 tons in Japan, German desulfurated plaster annual production, basically can both fully utilize, main application is to be used to produce building material product and cement retarder, China's plaster of paris is rich in minerals, desulfurated plaster is discarded mostly, the waste of a large amount of mechanical energies in the simultaneous dehydration backwater process.
The ammonia process of desulfurization, adopt ammonia, ammoniacal liquor or carbon ammonium as the sulfur dioxide absorbent, through the aeration oxidation to desulphurization circulating liquid, the ammonium sulfate of generation is descending with the rising desulfuration efficiency of concentration, need constantly to extract circulation fluid out and carry out evaporative crystallization, be lower than 30% with the sulphur ammonium concentration of keeping circulation fluid.Thereby process commonly used is the circulation fluid that will extract out to be introduced evaporimeter and carries out evaporative crystallization and obtain solid-state desulfurization product, and existing evaporimeter adopts steam as thermal source, and steam consumption quantity is bigger in the evaporation process.
More than two kinds of fume desulphurization methods commonly used, all adopt and after dedusting, to feed the desulfurizing tower bottom by flue gas, flue gas by a large amount of cleaning solution counter flow washings that contains alkaline absorbent, absorbs the sulfur in smoke washing in desulfurizing tower, thereby reduces the concentration of sulfur dioxide in flue gas.The temperature of circulation solution need be controlled at about 50 degrees centigrade in the wet desulfurizing process, thereby keep higher desulfuration efficiency with the solubility that keeps sulfur dioxide, reduce to outlet more than 150 degree Celsius of flue gas by desulfurizing tower inlet in sweetening process about 50 degrees centigrade, the reduction of temperature will lean on a large amount of evaporations of water to realize.The dehydration of desulfurization product simultaneously not only needs in new equipment input, the dehydration but also can increase the consumption of water once more, a large amount of mechanical energy of simultaneous or consumption of heat energy, energy consumption is big in the whole process, and the use amount of water is big, causes existing processes to be difficult for large-area promoting the use of.
Summary of the invention
At above defective, the purpose of this invention is to provide a kind of low investment low energy consumption flue gas wet desulphurization process, replace the desulfurization product dehydration equipment with smoke evaporative crystallizer; Utilize fume afterheat, replaced the energy consumption of desulfurization product dehydration, can produce tangible economic benefit.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of low energy consumption flue gas wet desulphurization process, adopt desulfurizing tower as apparatus for absorbing SO 2, the flue gas of handling through one-time dedusting in desulfurizing tower by with the circulating cleaning solution counter flow washing reaction that contains alkaline absorbent, remove sulfur in smoke, flue gas is the process smoke evaporative crystallizer before entering desulfurizing tower, in described smoke evaporative crystallizer, the alkaline absorbent of introducing from desulfurizing tower carries out reciprocal contacting with solution at the bottom of the reacted tower of sulfur dioxide with flue gas, utilizes fume afterheat that solution is evaporated and forms the solid recovery.
Further, the described alkaline absorbent that contains is powdered lime stone or lime.
Further, the described alkaline absorbent that contains is ammonia, ammoniacal liquor or carbon ammonium.
The whole service process can realize the interpolation of desulfurizing agent, the control of circulation fluid cleaning solution pH value and concentration, the control of the amount of evaporation by automatic control system.
Further, according to the difference of exhaust gas temperature, to circulation fluid cleaning solution further concentration of process before evaporating.
Wet desulfurizing process of the present invention, the waste heat that utilizes boiler smoke is as desulfurization reaction product gypsum or the Separation of Solid and Liquid of sulphur ammonium evaporation thermal source, for calcium is desulfurization, needn't adopt hydrocyclone and filter press or vacuum belt machine that final aqueous gypsum is carried out Separation of Solid and Liquid handles, directly adopt flue gas heat to evaporate and obtain solid-state product, because the generation of calcium sulfite is arranged in the evaporation process, reduced the purity of gypsum, do not reclaim available this technology under the situation of desulfurization product; For the ammonia process of desulfurization, obtain solid by utilizing fume afterheat that the desulfurization and dedusting product is evaporated, a small amount of ammonium sulfite that produces in evaporation process decomposes more than 60 degree, does not influence the purity of ammonium sulfate, the sulphur ammonium can be used as soil and fertilizer, play the effect in infertile field, saved investment, saved a large amount of steam, reduced the consumption of water in the whole process, energy-saving effect is remarkable, can be widely used in the desulfurization and dedusting of various boiler smokes, has good economic and social benefit.
Description of drawings
The present invention is described in further detail according to embodiment and accompanying drawing below.
Fig. 1 is the process chart of wet desulfurizing process of the present invention;
Fig. 2 is a smoke evaporative crystallizer principle assumption diagram of the present invention.
Among the figure: 1, desulfurizing tower; 2, smoke evaporative crystallizer; 3, oxidator; 4, PH detector; 5, cyclic water tank; 6, conveying worm; 7, agitator; 8, roots blower; 9, desulfurization product rear pump; 10, desulfuration recycle pump; 11, spraying layer; 12, demister.
21, smoke box; 22, smoke inlet; 23, exhanst gas outlet; 24, crystallization rod; 25, inlet; 26, cloth spills device; 27, taper Lower Hold.
The specific embodiment
Below with lime stone as desulfurizing agent, implementation of processes process of the present invention is described, its concrete technological process as shown in Figure 1, the flue gas of handling through one-time dedusting enters desulfurizing tower 1 through smoke evaporative crystallizer 2, and from the bottom of desulfurizing tower 1 from last, cyclic water tank 5 adopts conveying worm 6 input agstones and forms suitable slurries, PH detector 4 is housed on it, by desulfuration recycle pump 10, the cleaning solution that contains alkaline absorbent evenly spills cloth from spraying layer 11, both mix at desulfurization zone, sulfur in smoke and alkaline absorbent reaction, the flue gas that removes sulfur dioxide is after the demister 12 at desulfurizing tower 1 top is removed wherein aqueous water, and clean flue gas enters atmosphere through chimney; The bottom of desulfurizing tower 1 communicates with oxidator 3, adopts roots blower 8 bubbling airs to carry out oxidation, and is aided with agitator 7 and mixes, and its main chemical reactions is:
SO 2+H 2O→H 2SO 3→H ++HSO 3 -→2H ++SO 3 2-
CaCO 3+2H +→Ca 2++H 2O+CO 2
Ca 2++SO 3 2-→CaSO 3.1/2H 2O↓
HSO 3 -+1/2O 2→H ++SO 4 2-
Ca 2++SO 4 2-+2H 2O→CaSO 4.2H 2O↓
Fully after the reaction, adopt desulfurization product rear pump 9 to extract part circulation fluid (according to how many decisions of desulfurization product) and enter smoke evaporative crystallizer 2, remainder enters cyclic water tank 5 and continues to participate in circulation in the desulfurizing tower.The structural principle of smoke evaporative crystallizer 2 as shown in Figure 2, comprise a vertical smoke box 21 of installing, bottom and top have gas approach 22 and exhanst gas outlet 23, the bottom is provided with taper hold 27 as discharging opening, be horizontally installed with the crystallization rod 24 that many steel pipes are made in the smoke box 21, and along vertically staggered mutually, the top of crystallization rod 24 is equipped with the cloth that links to each other with inlet 25 and spills device 26.Gas approach 22 links to each other with boiler flue gas outlet, its exhanst gas outlet 23 links to each other with the smoke inlet of desulfurizing tower 2, when flue gas is flowed through smoke evaporative crystallizer 2, temperature can reach 150 degrees centigrade, and with crystallization rod 24 heating of installing in it, the solution cloth of coming through desulfurization product rear pump 10 spills in crystallization rod 24 surfaces, moisture content is corresponding to be evaporated, enter desulfurizing tower 1 together with flue gas, the corresponding gypsum product that stays falls within the taper hold 27 of smoke evaporative crystallizer 2, can regularly carry out collection and treatment.Satisfied on the one hand the curing of product, rationally utilized the waste heat of flue gas on the other hand, a large amount of savings the use of dehydration link electric energy.
Below be example with 10t/h boiler ammonia process of desulfurization engineering, prove its feasibility:
Coal-fired sulfur content is in 1% (Beijing 0.3%) desulfuration efficiency 97%;
10t/h boiler smoke amount is 30000m 3/ h, SO 2Concentration is 2000mg/m 3, the SO that per hour produces then 2Be 60kg;
SO 2Molecular weight is 64, (NH 4) 2SO 4Molecular weight is 132;
Desulfuration efficiency is that 97% o'clock desulfurizing tower per hour needs to absorb 58.2kg SO 2Corresponding generation sulphur ammonium 120Kg;
The solubility of ammonium sulfate is 850g/l (50 ℃ time)
The sulphur ammonium concentration is 25% o'clock, 1Kg water sulfur-bearing ammonium 0.333Kg;
The specific heat capacity of air is: 1.4kJ/kg;
Specific heat of water holds: 4.2kJ/kg;
1kg water is 2264kJ by 100 ℃ of heats that become the steam needs;
10t/h boiler smoke amount is 30000m 3/ h;
It is 210kJ that 1kg water rises to 100 ℃ of institute's calorific requirements by 50 ℃;
Liberated heat was when boiler smoke was reduced to 50 ℃ by 150 ℃ in one hour:
Flue gas specific heat capacity * decline temperature * flue gas quality=1.4kJ/kg * (150 ℃-50 ℃) * 30000m 3* 1.293kg/m 3=5430600kJ;
Can make the water of 5430600kJ/ (210kJ+2264kJ)=2195kg become steam from 50 ℃.
By above data as can be seen:
Can make the ammonium sulfate solution of concentration 25% separate out 730.9Kg sulphur ammonium crystal when evaporating the water of 2195Kg in one hour; And only have the sulphur ammonium of 120Kg to produce in one hour, and amount of redundancy is very big, even be lower than 50 degrees centigrade water and other a spot of thermal losses owing to replenish temperature in the pilot process, the evaporation of water amount is less than calculated value, but it is no problem fully to keep the operation of system.In the interpolation of whole service process by automatic control system realization desulfurizing agent, the control of circulation fluid cleaning solution pH value and concentration, the control of evaporation capacity.Also can to circulation fluid cleaning solution further concentration of process before evaporating, reduce the evaporation of water amount according to the difference of exhaust gas temperature.
With above identical, the operation of keeping system is also no problem fully for the calculating of calcium method desulfurization.
Adopt this described method of planting to carry out boiler flue gas desulfurization, can save a large amount of steam, reduced the consumption of water in the whole process, energy-saving effect is remarkable, can be widely used in the desulfurization and dedusting of various boiler smokes, has good economic and social benefit.

Claims (5)

1. low energy consumption flue gas wet desulphurization process, adopt desulfurizing tower as apparatus for absorbing SO 2, the flue gas of handling through one-time dedusting in desulfurizing tower by with the circulating cleaning solution counter flow washing reaction that contains alkaline absorbent, remove sulfur in smoke, it is characterized in that: flue gas is the process smoke evaporative crystallizer before entering desulfurizing tower, in described smoke evaporative crystallizer, the alkaline absorbent of introducing from desulfurizing tower carries out reciprocal contacting with solution at the bottom of the reacted tower of sulfur dioxide with flue gas, utilizes fume afterheat that solution is evaporated and forms the solid recovery.
2. low energy consumption flue gas wet desulphurization process according to claim 1 is characterized in that: the described alkaline absorbent that contains is powdered lime stone or lime.
3. low energy consumption flue gas wet desulphurization process according to claim 1 is characterized in that: the described alkaline absorbent that contains is ammonia, ammoniacal liquor or carbon ammonium.
4. according to described any low energy consumption flue gas wet desulphurization process of claim 1 to 3, it is characterized in that: in the interpolation of whole service process by automatic control system realization desulfurizing agent, the control of circulation fluid cleaning solution pH value and concentration, the control of evaporation capacity.
5. according to described any low energy consumption flue gas wet desulphurization process of claim 1 to 3, it is characterized in that: circulation fluid cleaning solution further concentration of process before evaporating.
CN201010133230A 2010-03-26 2010-03-26 Low energy consumption flue gas wet desulphurization process Pending CN101780368A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115045A (en) * 2010-11-30 2011-07-06 东营方圆有色金属有限公司 Method for concentrating and purifying dilute acid by using waste heat of smelting flue gas and device thereof
CN102658020A (en) * 2012-05-24 2012-09-12 首钢总公司 Ammonium-calcium dual-alkali flue gas desulfurization process
CN102949923A (en) * 2011-08-30 2013-03-06 威海鑫山集团有限公司 Method and device for removing sulfur dioxide in industrially-sintered flue gas and recovering gypsum
CN103977700A (en) * 2014-06-04 2014-08-13 长沙高必拓脱硫工程有限公司 Pneumatic emulsified limestone desulfurization system and process flow thereof
CN104671258A (en) * 2015-01-22 2015-06-03 张波 Method for producing compound fertilizer by using byproduct ammonium sulfate generated during ammonia-process desulfurizing of flue gas of boiler
CN104722193A (en) * 2015-03-06 2015-06-24 浙江蓝天求是环保股份有限公司 Independent circulating wet desulphurization system and method
CN104926008A (en) * 2014-03-18 2015-09-23 王辛平 Wet desulfurization wastewater zero emission process and device thereof
CN105833709A (en) * 2016-04-29 2016-08-10 东莞市恒升环保科技有限公司 Gas desulfuration device and desulfuration method
CN109179829A (en) * 2018-09-03 2019-01-11 清华大学 It is a kind of based on thermal method concentration divide salt without outlet self-sustaining desulfurization water round-robin method
CN109621705A (en) * 2018-12-12 2019-04-16 中石化广州工程有限公司 A kind of wet fuel gas desulfurizing technology of no discharging of waste liquid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN200998639Y (en) * 2007-02-09 2008-01-02 李培生 Concentrated crystallization and absorbed oxidation combined type ammonia process desulfuration tower
CN100364647C (en) * 2004-09-22 2008-01-30 上海弗卡斯环保工程有限公司 Ammonia type flue gas desulfurizing apparatus and its process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100364647C (en) * 2004-09-22 2008-01-30 上海弗卡斯环保工程有限公司 Ammonia type flue gas desulfurizing apparatus and its process
CN200998639Y (en) * 2007-02-09 2008-01-02 李培生 Concentrated crystallization and absorbed oxidation combined type ammonia process desulfuration tower

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115045A (en) * 2010-11-30 2011-07-06 东营方圆有色金属有限公司 Method for concentrating and purifying dilute acid by using waste heat of smelting flue gas and device thereof
CN102115045B (en) * 2010-11-30 2015-10-07 东营方圆有色金属有限公司 A kind of method utilizing flue gas during smelting waste heat thickening-purification technology diluted acid
CN102949923A (en) * 2011-08-30 2013-03-06 威海鑫山集团有限公司 Method and device for removing sulfur dioxide in industrially-sintered flue gas and recovering gypsum
CN102658020A (en) * 2012-05-24 2012-09-12 首钢总公司 Ammonium-calcium dual-alkali flue gas desulfurization process
CN104926008A (en) * 2014-03-18 2015-09-23 王辛平 Wet desulfurization wastewater zero emission process and device thereof
CN103977700A (en) * 2014-06-04 2014-08-13 长沙高必拓脱硫工程有限公司 Pneumatic emulsified limestone desulfurization system and process flow thereof
CN104671258A (en) * 2015-01-22 2015-06-03 张波 Method for producing compound fertilizer by using byproduct ammonium sulfate generated during ammonia-process desulfurizing of flue gas of boiler
CN104722193A (en) * 2015-03-06 2015-06-24 浙江蓝天求是环保股份有限公司 Independent circulating wet desulphurization system and method
CN105833709A (en) * 2016-04-29 2016-08-10 东莞市恒升环保科技有限公司 Gas desulfuration device and desulfuration method
CN109179829A (en) * 2018-09-03 2019-01-11 清华大学 It is a kind of based on thermal method concentration divide salt without outlet self-sustaining desulfurization water round-robin method
CN109621705A (en) * 2018-12-12 2019-04-16 中石化广州工程有限公司 A kind of wet fuel gas desulfurizing technology of no discharging of waste liquid

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