CN105251336B - Sodalime double alkali method double circulation desulphurization technique and system - Google Patents
Sodalime double alkali method double circulation desulphurization technique and system Download PDFInfo
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Abstract
The present invention discloses a kind of sodalime double alkali method double circulation desulphurization technique and system, and high-sulfur flue gas (SO can be realized mainly for providing one kind2＞ 10000mg/Nm3) purification and conventional flue gas SO2It is ultra-clean discharge and design.Sodalime double alkali method double circulation desulphurization technique of the present invention, including flue gas is inputted in reaction tower, the desulfurization of soda section, calcium method section desulfurization are carried out successively, are specially：Desulfurization is carried out to the sulfur dioxide in flue gas first with soda, the flue gas utilization calcium-base absorbing agent after sodium alkali desulfurization is then subjected to desulfurization, the flue gas after calcium-based desulfurization is discharged by demister；The soda clear liquid input soda regenerated reactor obtained after soda section desulfurization is collected, the calcium-based slurries obtained after calcium method section desulfurization is collected and partly or entirely inputs the progress soda regeneration of soda regenerated reactor.The present invention, the regenerative agent using the semi-saturation slurries in calcium method section desulfurization as soda clear liquid, soda carries out circulation desulfurization caused by life, realizes the mass circulation balance of whole system.
Description
Technical field
The present invention relates to the control of sulfur dioxide in industrial smoke, more particularly to the industrial smoke containing high-concentration sulfur dioxide
Deep purifying, the invention further relates to the technique and device for realizing such a deep purifying.
Background technology
Emphasis of the sulfur dioxide as the always environmental improvement of one of main source of atmospheric pollution in industrial smoke.At present
Commercial wide variety of technology is limestone-gypsum method.But because calcium-base absorbing agent and reaction product calcium sulfite are relatively low
Solubility, make the method easily fouling obstruction in generation system the problems such as, and since it is desired that higher liquid-gas ratio can be only achieved
Preferable sulfur dioxide removal efficiency, water consumption is very high, does not also apply to the processing of high-sulfur flue gas.In order to solve this problem, grind
The person of studying carefully proposes calcium and sodium double alkali method desulfurizing technology, and has industrially obtained popularization and application.Sodalime double alkali method is used as two using soda
The absorbent of sulfur oxide, enter the regenerated reactor outside tower after reaction generation sodium hydrogensulfite and sodium sulfite in reaction tower, with calcium
Base absorbant reaction regeneration retrieves soda.Due to high-dissolvability of the soda in water, to the high-selenium corn speed of sulfur dioxide,
The fouling obstructing problem of desulfurization method of limestone-gypsum is not only avoid, sweetening process can also be made in relatively low liquid-gas ratio condition
Lower progress, so as to reduce the size of reactor and system footprint area.But there is also many problems, such as high cost for the technology
Soda because side reaction consumption is excessive, limestone utilization is not high, is difficult to reach satisfied removing to high-concentration sulfur dioxide
Effect etc..
For these problems, Chinese patent CN200710067333 proposes a kind of segmented calcium and sodium double alkali method desulfurizing work
Skill, flue gas is first carried out preliminary purification with calcium-base absorbing agent in same reaction tower, then deep purifying is carried out with soda.But
The program is substantially calcium and sodium double alkali method desulfurizing device of having been connected after conventional limestone-gypsum desulfurizer, although saving
, problems with but be present in the dosage of soda：1) calcium method desulfurizer is an independent circulatory system, with conventional calcium method desulfurization
Device does not have difference, and preliminary desulfurization is carried out to flue gas by it, the problem of can not avoiding fouling in system and block, it is more difficult to suitable
Processing for high-sulfur flue gas；2) calcium method desulfurizer is compared to double alkali method desulfurizing system, and its liquid-gas ratio is much bigger, if first
Most of sulfur dioxide in flue gas is removed by the desulfurization of calcium method, the spray flux of calcium-base absorbing agent is significantly larger than soda absorbent, caused
Calcium method desulfurizer is also more much larger than double alkali method desulfurizing device, it is difficult to which two systems are connected in a reaction tower.3) it is single
From the point of view of double alkali method desulfurizing system itself, the utilization rate of calcium-base absorbing agent and soda is not improved.Chinese patent
CN201220288389 proposes a kind of double tower sulfur removal technology, (calcium sulfite, sulphur will be precipitated caused by sodium alkali desulfurization regenerative system
Sour calcium, calcium hydroxide etc.) preposition reaction tower is pumped into the preliminary desulfurization of flue gas progress as absorbent after dehydration, so as to improve calcium
The utilization rate of base absorbant, reduce the consumption of soda.But the technique still suffers from following problem：1) preposition reaction tower uses sodium
Sediment after the dehydration of alkali regenerated reactor as absorbent, block by the fouling that can not only make system generation even more serious, and to cigarette
Gas detergent power is extremely limited, considerably increases operating cost, has run counter to the original intention of Dual alkali technique；2) added using double tower
System complexity and floor space.3) it is not suitable for the purification of high-sulfur flue gas.
The content of the invention
In view of the above-mentioned problems, the present invention, which provides one kind, can reduce soda consumption, calcium-base absorbing agent utilization rate is improved, is avoided
The sodalime double alkali method double circulation desulphurization technique and system of scaling and obstruction.
To reach above-mentioned purpose, sodalime double alkali method double circulation desulphurization technique of the present invention, including flue gas is inputted in reaction tower,
The desulfurization of soda section, calcium method section desulfurization are carried out successively, are specially：Desulfurization is carried out to the sulfur dioxide in flue gas first with soda, so
The flue gas utilization calcium-base absorbing agent after sodium alkali desulfurization is subjected to desulfurization afterwards, the flue gas after calcium-based desulfurization passes through demister row
Go out；
The soda clear liquid input soda regenerated reactor obtained after soda section desulfurization is collected, collects the calcium obtained after calcium method section desulfurization
Based slurries partly or entirely input soda regenerated reactor and carry out soda regeneration.
Further, in addition to by the calcium sulfite precipitation in soda regenerated reactor separated, carry out oxidation dewater treatment
Technique obtains the gypsum of industrial use.
Specifically, the soda is sodium hydroxide and/or sodium carbonate.
Specifically, the calcium-base absorbing agent is calcium oxide, calcium hydroxide and/or lime stone.
Preferably, the pH value of the slurries in the calcium method absorption system is 5.5 to 6.5.
To reach above-mentioned purpose, sodalime double alkali method double circulation desulphurization system of the present invention, including a reaction tower, soda regenerated reactor
And soda liquid storage tank, calcium-base absorbing agent liquid storage tank, interior calcium method desulfurizer, the soda for being provided with upper and lower arrangement of the reaction tower
Method desulfurizer, wherein
The calcium method desulfurizer includes slurries collecting pit, is arranged on above the slurries collecting pit, is inhaled with the calcium base
The calcium method desulfurization spray equipment of agent liquid storage tank connection is received, the soda collecting pit connects soda by slurries conveyance conduit and regenerated
Pond；
The sodium alkali desulfurizer includes clear liquid collecting pit, is arranged on above the clear liquid collecting pit, with the soda
The sodium alkali desulfurization spray equipment of liquid storage tank connection, the soda collecting pit connect soda regenerated reactor by clear liquid conveyance conduit；
Exhanst gas outlet is provided with above the reaction tower, the smoke outlet is provided with demister, and the demister is arranged on
The top of calcium method desulfurization spray equipment.
Further, in addition to by the calcium sulfite precipitation in soda regenerated reactor separated, carry out oxidation dewater treatment
Obtain the gypsum of industrial use.
Sodalime double alkali method double circulation desulphurization technique and system of the present invention, due to soda in water good dissolubility, and
The speed of its sulfur dioxide absorption is very high, and under identical sulfur dioxide removal amount, the liquid-gas ratio calcium method of sodium alkali is much smaller,
Therefore main desulfurization task is undertaken by sodium alkali and preliminary purification first is carried out to flue gas, can be by sodium alkali desulfurizer and calcium method
Desulfurizer is designed to similar size, and is arranged in same reaction tower, can effectively reduce floor space and system is answered
Polygamy.
In addition, sodalime double alkali method double circulation desulphurization technique of the present invention and system, can be handled containing high-concentration sulfur dioxide (＞
10000mg/Nm3) industrial smoke, and deep purifying can be realized to conventional flue gas.
Brief description of the drawings
Fig. 1 is sodalime double alkali method double circulation desulphurization technique and system schematic of the present invention.
Embodiment
The present invention will be further described below in conjunction with the accompanying drawings.
Embodiment 1
The present embodiment sodalime double alkali method double circulation desulphurization technique, including flue gas is inputted in reaction tower, soda is carried out successively
Section desulfurization, calcium method section desulfurization, it is specially：Desulfurization is carried out to the sulfur dioxide in flue gas first with soda, then will pass through soda
Flue gas utilization calcium-base absorbing agent after desulfurization carries out desulfurization, and the flue gas after calcium-based desulfurization is discharged by demister；
The soda clear liquid input soda regenerated reactor obtained after soda section desulfurization is collected, collects the calcium obtained after calcium method section desulfurization
Based slurries partly or entirely input soda regenerated reactor and carry out soda regeneration, and remaining calcium-base absorbing agent continues cycling through desulfurization.
Be explained in detail in for：In soda section sweetening process, the soda supernatant fraction after desulfurization, which enters regenerated reactor, to be carried out again
Raw, remainder continues cycling through desulfurization.Soda caused by regeneration enters reaction tower circulation desulfurization by soda liquid storage tank, can basis
Soda, which is lost into soda liquid storage tank, supplements fresh soda.
In calcium method section sweetening process, the slurries after desulfurization, which are collected rear part or fully enter regenerated reactor, is used for soda
Regeneration, remaining slurries enter reaction tower circulation desulfurization by calcium method slurry pool, can be according to the losses of calcium method slurries to calcium method slurries
Fresh calcium-base absorbing agent is supplemented in pond.
The loop slurry come from calcium method section sweetening process is regenerating with the circulating clear liquid from sodium alkali desulphurization system
Being reacted in pond regenerates soda, and produces calcium sulfite precipitation and solidify sulfur dioxide.Calcium sulfite is separated laggard
The techniques such as row oxidation dewater treatment obtain the gypsum with industrial use.Soda caused by regeneration is followed into soda liquid storage tank
Ring desulfurization.
Technique described in the present embodiment, sodium alkali desulfurization and calcium method desulfurization are incorporated into a reactor, and utilized
The loop slurry of calcium method desulfurization regenerates to saturated absorption liquid caused by sodium alkali.It is preliminary net that flue gas first passes through soda progress
Change, then deep purifying is carried out by calcium-base absorbing agent, realize the efficient removal and soda, calcium-base absorbing agent of sulfur dioxide
The problems such as efficiently utilizing, and avoiding the fouling obstruction of calcium method desulfurization.
Semi-saturation slurries in calcium method section desulfurization are extracted out as regenerating alkali and enter soda regenerative system, sodium caused by regeneration
Alkali enters soda section sweetening process process and carries out circulation desulfurization, and saturated solution caused by soda system regenerates into regenerative system, from
And realize the mass circulation balance of whole system.
In technique described in the present embodiment, the setting range of the pH value of slurries can be 4-7 in calcium method absorption system, further
Can be preferably 5.5-6.5.Higher absorbent pH value can be realized to sulfur dioxide efficient removal,
Most of calcium-base absorbing agent, which only undergoes, once sprays desulfurization, or just enters after the seldom spray desulfurization of cycle-index
Regenerated reactor is used for the regeneration of soda.It so on the one hand can ensure calcium sulfite concentration very low in calcium-base absorbing agent, avoid
The problems such as fouling obstruction of system；On the other hand so that the calcium alkali concn in absorbent is very high all the time, it is ensured that to sulfur dioxide
Deep purifying and the effective regeneration to soda.
In technique described in the present embodiment, caused regeneration soda is returned in sodium alkali desulfurization system to participate in circulating and taken off in regenerated reactor
Sulphur, calcium sulfite precipitation produce gypsum by aoxidizing the subsequent techniques such as dehydration.
In technique described in the present embodiment, the consumption of calcium-base absorbing agent by desulfurization soda in suction regenerated reactor amount and PH
Value determines.When sulfur dioxide in flue gas concentration raises, increase the spray flux of soda, increase the concentration of soda solution, regenerated reactor
The amount of calcium-base absorbing agent required for middle soda regeneration also synchronously increases, and further make it that calcium base absorbs in calcium method desulphurization system
The increase of the magnitude of recruitment of the spray flux of agent and fresh calcium-base absorbing agent.Therefore two-step desulfurization system all improves the suction to sulfur dioxide
Receipts ability, so that the technique also has very strong adaptability to high-concentration sulfur dioxide, it is possible to achieve the height of high-sulfur flue gas
Effect purification.
Embodiment 2
As shown in figure 1, the present embodiment sodalime double alkali method double circulation desulphurization system, including a reaction tower, soda regenerated reactor with
And soda liquid storage tank, calcium-base absorbing agent liquid storage tank, interior calcium method desulfurizer, the sodium alkali for being provided with upper and lower arrangement of the reaction tower
Desulfurizer, wherein
The calcium method desulfurizer includes slurries collecting pit, is arranged on above the slurries collecting pit, is inhaled with the calcium base
The calcium method desulfurization spray equipment of agent liquid storage tank connection is received, the soda collecting pit connects soda by slurries conveyance conduit and regenerated
Pond；
The sodium alkali desulfurizer includes clear liquid collecting pit, is arranged on above the clear liquid collecting pit, with the soda
The sodium alkali desulfurization spray equipment of liquid storage tank connection, the soda collecting pit connect soda regenerated reactor by clear liquid conveyance conduit；
Exhanst gas outlet is provided with above the reaction tower, the smoke outlet is provided with demister, and the demister is arranged on
The top of calcium method desulfurization spray equipment.
The technical process of the present embodiment sodalime double alkali method double circulation desulphurization system is as follows：
In same reaction tower, flue gas first passes through sodium alkali desulfurizer and carries out preliminary desulfurization, sloughs most of dioxy
After changing sulphur, deep desulfuration is carried out into calcium method desulfurizer.Soda with part circulation desulfurization after smoke contacts, partly enter again
Raw pond returns in desulphurization system after being regenerated and continues to participate in reaction.Calcium-base absorbing agent in calcium method desulfurizer is by desulfurization
Afterwards, the regeneration of soda is wholly or largely used for into regenerated reactor, unnecessary part to carry out circulation desulfurization.In calcium method desulfurizer
The pH value that is set according to absorbent consumption and slurries of calcium-base absorbing agent supplemented in time.Soda is during circular regeneration
As partial loss occurs for the presence of side reaction, can be supplemented in time according to clear liquid amount in tower and PH setting values.
In reaction tower main body, sodium alkali desulfurization spray equipment 2 is placed in below reaction tower, and calcium method desulfurization spray equipment 3 is placed in
Above reaction tower.Below sodium alkali desulfurization spray equipment 2 is the clear liquid collecting pit 4 of sodium alkali desulfurization, and top is calcium method desulfurization
Slurries collecting pit 5, the top of calcium method desulfurization spray equipment 3 is demister 6.Flue gas enters from the smoke inlet positioned at reaction tower bottom
Enter, by the two-stage of soda and calcium-base absorbing agent spray, and by demister demisting after, flue is discharged into by exhanst gas outlet.Remove
Day with fog periodically carries out spraying-rinsing as needed
The soda part that clear liquid collecting pit 4 is collected is withdrawn into spray system 2 and carries out circulation desulfurization, and a part is pumped to
Soda regenerated reactor 7 is regenerated.The internal circulating load of soda is adjusted according to the concentration of sulfur dioxide in flue gas, when sulfur dioxide is dense
During degree rise, the increase of soda internal circulating load, when sulfur dioxide concentration reduces, soda internal circulating load reduces.It is extracted into the soda of regenerated reactor 7
Amount just adjusts according to the change of soda pH value, to ensure that the solution PH in clear liquid collecting pit 7 is stable in the range of service requirement.
The calcium-base absorbing agent that slurries collecting pit 5 is collected needs partly or entirely to be pumped to regenerated reactor 7 according to soda regeneration, remains
Remaining part point is pumped to the pulp storage tank 8 of storage calcium-base absorbing agent.During most calcium-base absorbing agent only live through and once spray
Desulfurization, or the spray desulfurization that cycle-index is seldom, it is ensured that higher calcium alkali concn and relatively low Asia in calcium-base absorbing agent
Calcium sulfate concentration.
According to the consumption of calcium-base absorbing agent and the change of pH value, fresh calcium-base absorbing agent is constantly supplemented into pulp storage tank 8
And process water, the calcium-base absorbing agent in pulp storage tank 8 are pumped to spray system 3 and carry out desulfurization.The higher pH value of calcium-base absorbing agent has
Beneficial to the removal efficiency for improving sulfur dioxide, PH general controls are in the range of 5.5-6.5 in operation
In regenerated reactor 7, alkaline reaction generation regeneration soda and calcium sulfite precipitation after calcium-base absorbing agent and desulfurization.
Regeneration soda is pumped to soda liquid storage tank 1, enters clear liquid collection with being supplemented in after the fresh soda and process water that come are mixed
Pond 4 participates in circulation desulfurization.Generation calcium sulfite precipitation be extracted after by subsequent oxidation dehydration etc. technique produce gypsum.
More than, only presently preferred embodiments of the present invention, but protection scope of the present invention is not limited thereto is any to be familiar with sheet
Those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in should all be covered
Within protection scope of the present invention.Therefore, protection scope of the present invention should be defined by the protection domain that claim is defined.
Claims (7)
1. a kind of sodalime double alkali method double circulation desulphurization technique, it is characterised in that including flue gas is inputted in reaction tower, carry out successively
The desulfurization of soda section, calcium method section desulfurization, it is specially：Desulfurization is carried out to the sulfur dioxide in flue gas first with soda, then will be passed through
Flue gas utilization calcium-base absorbing agent after sodium alkali desulfurization carries out desulfurization, and the flue gas after calcium-based desulfurization is discharged by demister；
The soda clear liquid input soda regenerated reactor obtained after soda section desulfurization is collected, collects the calcium base slurry obtained after calcium method section desulfurization
Liquid partly or entirely inputs soda regenerated reactor and carries out soda regeneration.
2. sodalime double alkali method double circulation desulphurization technique according to claim 1, it is characterised in that also include regenerating soda
In pond calcium sulfite precipitation separated, carry out aoxidize dewater treatment technique obtain the gypsum of industrial use.
3. sodalime double alkali method double circulation desulphurization technique according to claim 1, it is characterised in that the soda is hydroxide
Sodium and/or sodium carbonate.
4. sodalime double alkali method double circulation desulphurization technique according to claim 1, it is characterised in that the calcium-base absorbing agent is
Calcium oxide, calcium hydroxide and/or lime stone.
5. sodalime double alkali method double circulation desulphurization technique according to claim 1, it is characterised in that the calcium method absorption system
In slurries pH value be 5.5 to 6.5.
6. a kind of sodalime double alkali method double circulation desulphurization system, it is characterised in that including a reaction tower, soda regenerated reactor and soda
Liquid storage tank, calcium-base absorbing agent liquid storage tank, the interior calcium method desulfurizer provided with upper and lower arrangement of the reaction tower, sodium alkali desulfurization dress
Put, wherein
The calcium method desulfurizer includes slurries collecting pit, is arranged on above the slurries collecting pit, with the calcium-base absorbing agent
The calcium method desulfurization spray equipment of liquid storage tank connection, the soda collecting pit connect soda regenerated reactor by slurries conveyance conduit；
The sodium alkali desulfurizer includes clear liquid collecting pit, is arranged on above the clear liquid collecting pit, with the soda liquid storage
The sodium alkali desulfurization spray equipment of pond connection, the soda collecting pit connect soda regenerated reactor by clear liquid conveyance conduit；
Exhanst gas outlet is provided with above the reaction tower, the smoke outlet is provided with demister, and the demister is arranged on calcium method
The top of desulfurization spray equipment；
Flue gas is inputted in reaction tower, the sulfur dioxide in flue gas taken off using soda in the sodium alkali desulfurizer
Sulphur, the soda clear liquid obtained after desulfurization input soda regenerated reactor, and then flue gas utilizes calcium base to inhale into the calcium method desulfurizer
Receive agent and carry out desulfurization, collect the calcium-based slurries obtained after desulfurization and partly or entirely input the progress soda regeneration of soda regenerated reactor, warp
Flue gas after calcium-based desulfurization is discharged by demister.
7. sodalime double alkali method double circulation desulphurization system according to claim 6, it is characterised in that also include regenerating soda
In pond calcium sulfite precipitation separated, carry out aoxidize dewater treatment obtain the gypsum of industrial use.
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| CN105854551A (en) * | 2016-05-19 | 2016-08-17 | 大唐环境产业集团股份有限公司 | Double-alkali double-circulation desulfurization absorption system and method |
| CN105879623A (en) * | 2016-05-19 | 2016-08-24 | 大唐环境产业集团股份有限公司 | Dual-alkali and dual-circulation collaborative desulfurization and denitrification system and method |
| CN109692550A (en) * | 2019-01-25 | 2019-04-30 | 鲍可可 | A kind of circulation sodium method flue gas desulfurization technique |
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| CA1129181A (en) * | 1979-03-30 | 1982-08-10 | Mark Richman | So.sub.2 scrubbing system for flue gas desulfurization |
| US5520897A (en) * | 1993-08-16 | 1996-05-28 | The Babcock & Wilcox Company | Method of reagent and oxidation air delivery |
| JP3573950B2 (en) * | 1997-06-24 | 2004-10-06 | 東洋エンジニアリング株式会社 | Exhaust gas desulfurization method |
| CN1212879C (en) * | 2003-07-10 | 2005-08-03 | 浙江大学 | Concentrated alkali double alkali method stack gas desulfurizing technology |
| CN100469419C (en) * | 2007-02-13 | 2009-03-18 | 浙江天蓝脱硫除尘有限公司 | Segmented calcium and sodium double alkali method desulfurizing technology and device thereof |
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