CN102485324B - The method of sulphur ammonium-limestone-based process flue gas desulfurization - Google Patents

The method of sulphur ammonium-limestone-based process flue gas desulfurization Download PDF

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CN102485324B
CN102485324B CN201110106205.4A CN201110106205A CN102485324B CN 102485324 B CN102485324 B CN 102485324B CN 201110106205 A CN201110106205 A CN 201110106205A CN 102485324 B CN102485324 B CN 102485324B
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flue gas
tower
absorbent
desulfurization
absorption
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CN102485324A (en
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陶俊
徐继红
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Anhui University of Science and Technology
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Anhui University of Science and Technology
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Abstract

A method for sulphur ammonium-limestone-based process flue gas desulfurization, more particularly, be a kind of be raw material with lime stone, ammonium sulfate is the Wet-type desulfuration method of process absorbent.Comprise the following steps: take percentage by weight as the ammonium sulfate of 5 ~ 40% be process absorbent, with lime stone (calcium carbonate) for absorbent, flue gas enters and absorbing liquid counter current contacting mass transfer in the middle part of absorption tower, leave from tower top, tower bottom divides slurries to circulate in absorption tower, fraction slurries send desulfurization slag to dewater, and desulfurization slag dewatering process water returns absorption system.The invention has the beneficial effects as follows: desulfuration absorbing tower rate of sulphur expulsion is accelerated, and identical tower can process more flue gas; Absorption tower operating flexibility is large, stable operation, and operation energy consumption is low; Partial denitrification is reached while desulfurization; Desulfurization slag postprocessing working procedures retains larger integral utilization space, comprises and establishes calcination process to reclaim sulfur dioxide.

Description

The method of sulphur ammonium-limestone-based process flue gas desulfurization
Technical field
The invention belongs to boiler exhaust gas process field.The present invention relates to a kind of method removing sulfur dioxide, more particularly, be a kind of be raw material with lime stone, ammonium sulfate is the Wet-type desulfuration method of process absorbent.
Background technology
The energy resource structure more than 90% of China is using fire coal as power, and burning coal all can produce SO 2, wherein maximum with power plant emission amount, by SO 2for the Acid Rain Pollution hazard area caused by main has accounted for about 40% of area, the whole nation is annual therefore and the economic loss caused has reached and exceeds 100 billion.
At present, the method for flue gas desulfurization has in the world reached kind more than 100, and the method for industrial application also about has 20 kinds.Wherein Wet Flue Gas Desulfurization Technique application accounts for about 85% of whole industrialization desulfurizer, and Wet Limestone/lime method accounts for about 80% of wet method, occupies an leading position in current technology.This technology blasts air in the slurries on absorption tower, washs flue gas with lime stone, forces to make CaSO 3be oxidized to CaSO 4(gypsum).
Lime/gypsum method Patents is as follows:
CN99113914 discloses a kind of lime/gypsum method flue gas desulfurization technique, the steps include: (1) dedusting, (2) desulfurization, and (3) make the mixed liquor containing gypsum crystallization body, (4) dehydration by-product gypsum.Wherein desulfurization is that flue gas after dedusting is entered desulfurizing tower again after booster fan warp let-off humidification cooler, in tower, make secondary desulfuration again through porous plate bubbling flue gas after desulfurization through spray liquid, after purification, flue gas enters chimney again after tower top gas-liquid separator separates after flue gas heater.
CN1923338 discloses a kind of flue gas desulfurization technique, particularly a kind of fume desulfurizing process with enhancement limestone method, be mainly used in air contaminant treatment, Prevention Technique field, comprise: lime stone and additive are inputted digestion reactor respectively, react to generate with water and absorb slurries at digestion reactor sodalime stone and additive mixing; To absorb slurries input absorption tower, sulfur-containing smoke gas enters absorption tower, and after absorption slurry reaction, purifying smoke discharges absorption tower; The absorption slurries absorbing sulfur dioxide are discharged Posterior circle use or go post processing bottom absorption tower.
Limestone/gypsum method, blasts air in the slurries on absorption tower, adds the load on absorption tower on the one hand, and oxidation air blockage fractures and often occurs on the other hand, covers with shade to the application of this method.Be exactly that accessory substance gypsum does not reach application grade in addition, generally abandon as refuse, operating cost is high all becomes restraining factors.Above-mentioned limestone/gypsum method desulfuration efficiency is higher, but is difficult to improve desulfuration efficiency further.
Summary of the invention
The object of the present invention is to provide a kind of method removing sulfur dioxide from flue gas, change sweetening process, do not establish oxidation fan, reduce desulphurization cost, improve lime/gypsum method desulfuration efficiency, improve by-product integral utilization space.
Method of the present invention is that to absorb percentage by weight that liquid phase is benchmark be the ammonium sulfate of 5 ~ 40% is process absorbent, with lime stone (calcium carbonate) for absorbent, flue gas enters and absorbing liquid counter current contacting mass transfer in the middle part of absorption tower, leave from tower top, tower bottom divides slurries to circulate in absorption tower, fraction slurries send desulfurization slag to dewater, and desulfurization slag dewatering process water returns absorption system.
The present invention be embodied in following some: in (1) absorbent, ammonium sulphate content is large, and percentage by weight reaches 5 ~ 40%, and participate in absorption reaction process, but finally get back to ammonium sulfate state, therefore ammonium sulfate is called process absorbent.(2) lime stone (calcium carbonate) not directly react with sulfur dioxide, but in whole reaction, consumes lime stone and sulfur dioxide absorption, and generation calcium sulfite discharge system, therefore lime stone is called absorbent.(3) ammonium sulfate liquid is as process absorbent, plays the effect of buffer solution, and the pH value of system is relatively stable, and system has larger operating flexibility; Ammonium sulfate liquid, as process absorbent, plays the effect of hydrotropy lime stone, makes lime stone react more complete; (4) using ammonium sulfate as process absorbent, can partial denitrification while desulfurization; (5) desulfurization slag main component is calcium sulfite, improves by-product integral utilization space.
Specific implementation process of the present invention is as follows:
Whole desulphurization reaction can be divided into 6 steps: (1) sulfur dioxide in flue gas enters liquid phase by gas phase, is combined into sulfurous acid with water; (2) sulfurous acid and ammonium sulfate liquid react and generate ammonium hydrogen sulfate and ammonium bisulfite; (3) ammonium sulfate makes calcium carbonate accelerate to decompose, and generates ammonia simultaneously; (4) ammonium hydrogen sulfate and ammonium bisulfite and ammonia generation neutralization reaction generate ammonium sulfate and ammonium sulfite respectively; (5) ammonium sulfite and calcium sulfate effect generate calcium sulfite; (6) calcium sulfite oxidation generates calcium sulfate, and sulfite oxidation generates ammonium sulfate.
Often walk corresponding reaction equation as follows:
SO 2+H 2O=H 2SO 3(1)
(NH 4) 2SO 4+H 2SO 3=NH 4HSO 4+NH 4HSO 3(2)
CaCO 3+CO 2+H 2O=Ca(HCO 3) 2(3-1)
(NH 4) 2SO 4+Ca(HCO 3) 2=CaSO 4+2NH 3+2CO 2+2H 2O(3-2)
(NH 4) 2SO 4+CaCO 3=CaSO 4+2NH 3+CO 2+H 2O(3-3)
NH 4HSO 4+NH 3=(NH 4) 2SO 4(4-1)
NH 4HSO 3+NH 3=(NH 4) 2SO 3(4-2)
(NH 4) 2SO 3+CaSO 4=(NH 4) 2SO 4+CaSO 3(5)
Denitration reaction can be divided into four steps: (7) oxidation of nitric oxide generates nitrogen dioxide; (8) nitrogen dioxide and water react and generate nitrous acid; (8) nitrous acid and ammonia react generate ammonium nilrite; (10) ammonium nilrite decomposes.Corresponding reaction equation is as follows:
NO 2+NO+H 2O=2HNO 2(8)
NH 3+HNO 2=NH 4NO 2(9)
NH 4NO 2=N 2+2H 2O(10)
Accompanying drawing explanation
Accompanying drawing 1 is embodiment 1 schematic diagram
Detailed description of the invention
Example 1
Absorption tower 1 in Fig. 1, circulating pump 2, slush pump 3, cyclone 4, filter press 5, limestone slurry liquid bath 6, limestone slurry liquid pump 7, type washing trough 8, washing water pump 9.Flue gas A, purifying smoke B, fresh water (FW) C, desulfurization slag (calcium sulfite) D, lime stone (calcium carbonate) E
Flow is 200000Nm 3/ h, temperature is that first the flue gas A of 150 DEG C enters in the middle part of desulfuration absorbing tower 1, contacts with the circulation fluid under spraying from top, and in circulation fluid, the concentration of ammonium sulfate is 20% (mass fraction), tower prime cement liquid realizes circulation by slush pump 2, and recycle slurry liquid measure is 480m 3/ h; Lime stone E throws absorption tower into limestone slurry liquid pump 7 make 10% (mass fraction) liquid slurry in limestone slurry liquid bath 6 after, pass through spray washing, sulfur dioxide in flue gas, dust are removed, then through tower top 50 DEG C of washings washings, purifying smoke B leaves absorption system and send chimney.Desulfurizing tower lower groove body slurry temperature about 85 DEG C, fraction slurries drains into separation circuit by slush pump.
Flow is 20m 3the slurries of/h squeeze into cyclone 4 by slush pump 3, through cyclonic separation, cyclone separator 4 underflow send filter press 5 filter and wash, pressing filtering liquid, merge send limestone slurry liquid bath 6 with eddy flow top liquid, washing fresh water (FW) C washing press filter cake, be collected in washing liquid bath 8, send absorption tower demisting by washing liquid pump 9, press filtration solid phase is that desulfurization slag (calcium sulfite) D send postprocessing working procedures.
In limestone slurry liquid bath 6, add the lime stone E of 720Kg/h, with from separation circuit pressing filtering liquid, with the liquid slurrying of eddy flow top, in slurries, calcium carbonate content is 10%, sends into absorption tower 1 by limestone slurry liquid pump 7.
The invention has the beneficial effects as follows: desulfuration absorbing tower rate of sulphur expulsion is accelerated, and identical tower can process more flue gas; Absorption tower operating flexibility is large, stable operation, and operation energy consumption is low; Partial denitrification is reached while desulfurization; Desulfurization slag postprocessing working procedures retains larger integral utilization space, comprises and establishes calcination process to reclaim sulfur dioxide.

Claims (4)

1. a method for sulphur ammonium-limestone-based process flue gas desulfurization, is characterized in that: with absorb percentage by weight that liquid phase is benchmark be the ammonium sulfate of 5 ~ 40% for process absorbent, participate in absorption reaction process, but finally get back to ammonium sulfate state; Take lime stone as absorbent, lime stone does not have directly and sulfur dioxide reacts, but in whole reaction, consumes lime stone and sulfur dioxide absorption, generates calcium sulfite and discharges system; Flue gas enters and absorbing liquid counter current contacting mass transfer in the middle part of absorption tower, leaves from tower top, and at the bottom of tower, major part slurries circulate in absorption tower, and small part slurries send gypsum dehydration, and gypsum dehydration fresh water (FW) returns absorption system.
2. the method for sulphur ammonium-limestone-based process flue gas desulfurization according to claim 1, is characterized in that: ammonium sulfate liquid, as process absorbent, plays the effect of buffer solution, and the pH value of system is relatively stable, and system has larger operating flexibility; Ammonium sulfate liquid, as process absorbent, plays the effect of hydrotropy lime stone, makes lime stone react more complete.
3. the method for sulphur ammonium-limestone-based process flue gas desulfurization according to claim 1, is characterized in that: using ammonium sulfate as process absorbent, can partial denitrification while desulfurization.
4. the method for sulphur ammonium-limestone-based process flue gas desulfurization according to claim 1, is characterized in that: desulfurization slag main component is calcium sulfite, improves by-product integral utilization space.
CN201110106205.4A 2011-04-15 2011-04-15 The method of sulphur ammonium-limestone-based process flue gas desulfurization Active CN102485324B (en)

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CN104496605B (en) * 2014-12-24 2017-06-06 金正大诺泰尔化学有限公司 The method and device of sulphur dioxide production alkaline fertilizer in a kind of recycling furnace gas
CN109647152A (en) * 2019-01-29 2019-04-19 中南大学 A kind of purification method and its purification device containing chlorine or/and sulphur-containing exhaust gas

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0295908A2 (en) * 1987-06-17 1988-12-21 Bechtel Group Incorporated Flue gas desulfurization
CN1194176A (en) * 1997-03-21 1998-09-30 沈阳环境科学研究所 New technology for absorbing and eliminating sulfur dioxide in smoke chemically
CN1358109A (en) * 2000-01-14 2002-07-10 三菱重工业株式会社 Exhaust gas desulfurizing method and system therefor
CN1923339A (en) * 2006-08-18 2007-03-07 浙江天蓝脱硫除尘有限公司 Fume desulfurizing process with enhancement lime method
CN101422688A (en) * 2008-11-07 2009-05-06 浙江大学 Ammonia-ammonium sulphate wet-method flue-gas desulfurization and ammonium sulphate recovery technique using induced crystallization

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0295908A2 (en) * 1987-06-17 1988-12-21 Bechtel Group Incorporated Flue gas desulfurization
CN1194176A (en) * 1997-03-21 1998-09-30 沈阳环境科学研究所 New technology for absorbing and eliminating sulfur dioxide in smoke chemically
CN1358109A (en) * 2000-01-14 2002-07-10 三菱重工业株式会社 Exhaust gas desulfurizing method and system therefor
CN1923339A (en) * 2006-08-18 2007-03-07 浙江天蓝脱硫除尘有限公司 Fume desulfurizing process with enhancement lime method
CN101422688A (en) * 2008-11-07 2009-05-06 浙江大学 Ammonia-ammonium sulphate wet-method flue-gas desulfurization and ammonium sulphate recovery technique using induced crystallization

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