CN105251336A - Soda-lime-double-alkali-method double-circulation desulfurization technology and system - Google Patents
Soda-lime-double-alkali-method double-circulation desulfurization technology and system Download PDFInfo
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Abstract
The invention discloses a soda-lime-double-alkali-method double-circulation desulfurization technology and system. The technology and system are designed mainly for achieving purification of high-sulfur flue gas (SO2 is larger than 10,000 mg/Nm<3>) and SO2 ultraclean emission of conventional flue gas. The soda-lime-double-alkali-method double-circulation desulfurization technology includes the steps that the flue gas is input into a reaction tower and sequentially subjected to sodium-alkali-section desulfurization and calcium-method-section desulfurization, and includes the specific steps that sulfur dioxide in the flue gas is desulfurized through sodium alkali, then the flue gas obtained after being desulfurized through the sodium alkali is desulfurized through calcium-based sorbents, and the flue gas obtained after calcium-based desulfurization is discharged through a demister; sodium-alkali clear liquid obtained after sodium-alkali-section desulfurization is collected and input into a sodium-alkali regeneration pond, and part or all of calcium-based slurry obtained after calcium-method-section desulfurization is input into the sodium-alkali regeneration pond to carry out sodium-alkali regeneration. According to the soda-lime-double-alkali-method double-circulation desulfurization technology and system, the subsaturation slurry in the calcium-method-section desulfurization serves as regenerants of the sodium-alkali clear liquid, generated sodium alkali is subjected to circulation desulfurization, and the mass circulation balance of the whole system is achieved.
Description
Technical field
The present invention relates to the control of sulfur dioxide in industrial smoke, particularly relate to the deep purifying containing high-concentration sulfur dioxide industrial smoke, the invention still further relates to the technique and device that realize this kind of deep purifying.
Background technology
Sulfur dioxide in industrial smoke is the emphasis of environmental improvement as one of main source of atmospheric pollution always.The technology of current commercial extensive use is limestone-gypsum method.But because calcium-base absorbing agent and the lower solubility of product calcium sulfite, make the problems such as the fouling obstruction in the easy generation systems of this method, and because need higher liquid-gas ratio just can reach desirable sulfur dioxide removal efficiency, water consumption is very high, also the process of inapplicable high-sulfur flue gas.In order to address this problem, researcher proposes calcium and sodium double alkali method desulfurizing technology, and industrially obtains and apply.Sodalime double alkali method is using soda as the absorbent of sulfur dioxide, and in reaction tower, reaction enters the regenerated reactor outside tower after generating sodium hydrogensulfite and sodium sulfite, again obtains soda with calcium-base absorbing agent reaction regeneration.Due to the high-dissolvability of soda in water, to the high-selenium corn speed of sulfur dioxide, not only avoid the fouling obstructing problem of desulfurization method of limestone-gypsum, sweetening process can also be made to carry out under lower liquid-gas ratio condition, thus reduce size and the system footprint area of reactor.But this technology also exists many problems, if the soda of high cost is because side-reaction consumes is too much, limestone utilization is not high, is difficult to reach satisfied removal effect etc. to high-concentration sulfur dioxide.
For these problems, Chinese patent CN200710067333 proposes a kind of segmented calcium and sodium double alkali method desulfurizing technology, makes flue gas first carry out preliminary purification with calcium-base absorbing agent in same reaction tower, then carries out deep purifying with soda.But the program is calcium and sodium double alkali method desulfurizing device of having connected after conventional limestone-gypsum desulfurizer in essence, although save the consumption of soda, but there is following problem: 1) calcium method desulfurizer is an independently circulatory system, difference is not had with conventional calcium method desulfurizer, by it, preliminary desulfurization is carried out to flue gas, the problem of fouling and obstruction in system cannot be avoided, be more difficult to the process being applicable to high-sulfur flue gas; 2) calcium method desulfurizer is compared to double alkali method desulfurizing system, its liquid-gas ratio is much bigger, if first remove most of sulfur dioxide in flue gas by the desulfurization of calcium method, the spray flux of calcium-base absorbing agent will much larger than soda absorbent, cause calcium method desulfurizer also much larger than double alkali method desulfurizing device, be difficult to two cover systems to be connected in a reaction tower.3) single with regard to double alkali method desulfurizing system self, 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, by the precipitation (calcium sulfite that sodium alkali desulfurization regenerative system produces, calcium sulfate, calcium hydroxide etc.) pump into preposition reaction tower as absorbent preliminary desulfurization is carried out to flue gas after dehydration, thus improve the utilization rate of calcium-base absorbing agent, decrease the consumption of soda.But this technique still there are the following problems: 1) preposition reaction tower adopts the sediment after the dehydration of soda regenerated reactor as absorbent, not only can make system that even more serious fouling occurs to block, and it is very limited to gas cleaning ability, considerably increase operating cost, run counter to the original intention of Dual alkali technique; 2) double tower is adopted to add system complexity and floor space.3) purification of high-sulfur flue gas is not suitable for.
Summary of the invention
For the problems referred to above, the invention provides one and can reduce soda consumption, improve calcium-base absorbing agent utilization rate, avoid sodalime double alkali method double circulation desulphurization technique and the system of scaling and obstruction.
For achieving the above object, sodalime double alkali method double circulation desulphurization technique of the present invention, comprise and flue gas is inputted in reaction tower, carry out the desulfurization of soda section, the desulfurization of calcium method section successively, be specially: first utilize soda to carry out desulfurization to the sulfur dioxide in flue gas, then the flue gas utilization calcium-base absorbing agent after sodium alkali desulfurization is carried out desulfurization, the flue gas after calcium-based desulfurization is discharged through demister;
The soda clear liquid input soda regenerated reactor obtained after collecting the desulfurization of soda section, the calcium-based slurries obtained after collecting the desulfurization of calcium method section partly or entirely inputs soda regenerated reactor and carries out soda regeneration.
Further, also comprise and the calcium sulfite precipitation in soda regenerated reactor is carried out being separated, carrying out being oxidized the gypsum that processed technique obtains industrial use.
Particularly, described soda is NaOH and/or sodium carbonate.
Particularly, described calcium-base absorbing agent is calcium oxide, calcium hydroxide and/or lime stone.
Preferably, the pH value of the slurries in described calcium method absorption system is 5.5 to 6.5.
For achieving the above object, sodalime double alkali method double circulation desulphurization system of the present invention, comprise a reaction tower, soda regenerated reactor and soda liquid storage tank, calcium-base absorbing agent liquid storage tank, be provided with calcium method desulfurizer, the sodium alkali desulfurizer of upper and lower layout in described reaction tower, wherein
Described calcium method desulfurizer comprises slurries collecting pit, is arranged on above described slurries collecting pit, the calcium method desulfurization spray equipment be communicated with described calcium-base absorbing agent liquid storage tank, and described soda collecting pit is communicated with soda regenerated reactor by slurries conveyance conduit;
Described sodium alkali desulfurizer comprises clear liquid collecting pit, is arranged on above described clear liquid collecting pit, the sodium alkali desulfurization spray equipment be communicated with described soda liquid storage tank, and described soda collecting pit is communicated with soda regenerated reactor by clear liquid conveyance conduit;
Be provided with exhanst gas outlet above described reaction tower, described smoke outlet is provided with demister, and described demister is arranged on the top of calcium method desulfurization spray equipment.
Further, also comprise and the calcium sulfite precipitation in soda regenerated reactor is carried out being separated, carry out being oxidized processed and obtain the gypsum of industrial use.
Sodalime double alkali method double circulation desulphurization technique of the present invention and system, due to the dissolubility that soda is good in water, and the speed of its sulfur dioxide absorption is very high, under identical sulfur dioxide removal amount, the liquid-gas ratio calcium method of sodium alkali is much smaller, therefore bear main desulfurization task by sodium alkali and first preliminary purification is carried out to flue gas, sodium alkali desulfurizer can be designed to similar size with calcium method desulfurizer, and be arranged in same reaction tower, can effectively reduce floor space and system complexity.
In addition, sodalime double alkali method double circulation desulphurization technique of the present invention and system, can process containing high-concentration sulfur dioxide (> 10000mg/Nm
3) industrial smoke, and deep purifying can be realized to conventional flue gas.
Accompanying drawing explanation
Fig. 1 is sodalime double alkali method double circulation desulphurization technique of the present invention and system schematic.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention will be further described.
Embodiment 1
The present embodiment sodalime double alkali method double circulation desulphurization technique, comprise and flue gas is inputted in reaction tower, carry out the desulfurization of soda section, the desulfurization of calcium method section successively, be specially: first utilize soda to carry out desulfurization to the sulfur dioxide in flue gas, then the flue gas utilization calcium-base absorbing agent after sodium alkali desulfurization is carried out desulfurization, the flue gas after calcium-based desulfurization is discharged through demister;
The soda clear liquid input soda regenerated reactor obtained after collecting the desulfurization of soda section, the calcium-based slurries obtained after collecting the desulfurization of calcium method section partly or entirely inputs soda regenerated reactor and carries out soda regeneration, and residue calcium-base absorbing agent continues circulation desulfurization.
Be interpreted as particularly: in soda section sweetening process, the soda supernatant fraction after desulfurization enters regenerated reactor and regenerates, and remainder continues circulation desulfurization.The soda that regeneration produces enters reaction tower circulation desulfurization by soda liquid storage tank, can supplement fresh soda according to soda loss in soda liquid storage tank.
In calcium method section sweetening process, slurries after desulfurization are collected rear section or all enter the regeneration of regenerated reactor for soda, residue slurries enter reaction tower circulation desulfurization by calcium method slurry pool, can supplement fresh calcium-base absorbing agent according to the loss of calcium method slurries in calcium method slurry pool.
Come from loop slurry in calcium method section sweetening process to react in regenerated reactor with the circulating clear liquid from sodium alkali desulphurization system soda regenerate, and produce calcium sulfite and precipitate sulfur dioxide is solidified.Calcium sulfite carries out being oxidized the techniques such as processed and obtains the gypsum with industrial use after separating.The soda that regeneration produces enters soda liquid storage tank and carries out circulation desulfurization.
Technique described in the present embodiment, is incorporated into sodium alkali desulfurization and the desulfurization of calcium method in a reactor, and utilizes the loop slurry of calcium method desulfurization to regenerate the saturated absorption liquid that sodium alkali produces.Flue gas first carries out preliminary purification by soda, then carries out deep purifying by calcium-base absorbing agent, achieves the efficiency utilization of the efficient removal of sulfur dioxide and soda, calcium-base absorbing agent, and avoids the problems such as the fouling obstruction of calcium method desulfurization.
Semi-saturation slurries in the desulfurization of calcium method section are extracted out as regenerating alkali and enters soda regenerative system, the soda that regeneration produces enters soda section sweetening process process and carries out circulation desulfurization, the saturated solution that soda system produces enters regenerative system regeneration, thus realizes the mass circulation balance of whole system.
In technique described in the present embodiment, in calcium method absorption system, the setting range of the pH value of slurries can be 4-7, further can be preferably 5.5-6.5.Higher absorbent pH value can realize sulfur dioxide efficient removal,
Major part calcium-base absorbing agent only experiences and once sprays desulfurization, or just enters the regeneration of regenerated reactor for soda after the little spray desulfurization of cycle-index.Such one side can ensure calcium sulfite concentration very low in calcium-base absorbing agent, avoids the problems such as the fouling obstruction of system; On the other hand, make the calcium alkali concn in absorbent very high all the time, ensure that the deep purifying to sulfur dioxide and the effective regeneration to soda.
In technique described in the present embodiment, the regeneration soda produced in regenerated reactor is got back in sodium alkali desulfurization system and is participated in circulation desulfurization, and calcium sulfite precipitation waits subsequent technique to produce gypsum by oxidation dehydration.
In technique described in the present embodiment, the consumption of calcium-base absorbing agent is determined by the amount of desulfurization soda in suction regenerated reactor and pH value.When sulfur dioxide in flue gas concentration raises, increase the spray flux of soda, increase the concentration of soda solution, the amount of the calcium-base absorbing agent in regenerated reactor required for soda regeneration also synchronously increases, and further makes the spray flux of calcium-base absorbing agent in calcium method desulphurization system and the magnitude of recruitment of fresh calcium-base absorbing agent increase.Therefore two-step desulfurization system all improves the absorbability to sulfur dioxide, thus makes this technique also have very strong adaptive capacity to high-concentration sulfur dioxide, can realize the high-efficient purification of high-sulfur flue gas.
Embodiment 2
As shown in Figure 1, the present embodiment sodalime double alkali method double circulation desulphurization system, comprise a reaction tower, soda regenerated reactor and soda liquid storage tank, calcium-base absorbing agent liquid storage tank, be provided with calcium method desulfurizer, the sodium alkali desulfurizer of upper and lower layout in described reaction tower, wherein
Described calcium method desulfurizer comprises slurries collecting pit, is arranged on above described slurries collecting pit, the calcium method desulfurization spray equipment be communicated with described calcium-base absorbing agent liquid storage tank, and described soda collecting pit is communicated with soda regenerated reactor by slurries conveyance conduit;
Described sodium alkali desulfurizer comprises clear liquid collecting pit, is arranged on above described clear liquid collecting pit, the sodium alkali desulfurization spray equipment be communicated with described soda liquid storage tank, and described soda collecting pit is communicated with soda regenerated reactor by clear liquid conveyance conduit;
Be provided with exhanst gas outlet above described reaction tower, described smoke outlet is provided with demister, and described 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 carries out preliminary desulfurization through sodium alkali desulfurizer, after sloughing most of sulfur dioxide, enters calcium method desulfurizer and carries out deep desulfuration.Soda with smoke contacts rear section circulation desulfurization, part enters to get back to after regenerated reactor regenerates in desulphurization system and continues to participate in reaction.Calcium-base absorbing agent in calcium method desulfurizer is after desulfurization, and whole or major part enters the regeneration of regenerated reactor for soda, and unnecessary part carries out circulation desulfurization.Calcium-base absorbing agent in calcium method desulfurizer supplements in time according to the pH value of absorbent consumption and slurries setting.Soda in circular regeneration process also can because of side reaction exist generating portion loss, can supplement in time according to clear liquid amount in tower and PH setting value.
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.Is the clear liquid collecting pit 4 of sodium alkali desulfurization below sodium alkali desulfurization spray equipment 2, and top is the slurries collecting pit 5 of calcium method desulfurization, is demister 6 above calcium method desulfurization spray equipment 3.Flue gas enters from the smoke inlet being positioned at reaction tower bottom, and the two-stage through soda and calcium-base absorbing agent sprays, and by after demister demist, is discharged enter flue by exhanst gas outlet.Demister periodically carries out spraying-rinsing
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 and regenerates.The internal circulating load of soda adjusts according to the concentration of sulfur dioxide in flue gas, and when sulfur dioxide concentration raises, soda internal circulating load increases, and when sulfur dioxide concentration reduces, soda internal circulating load reduces.The soda amount being extracted into regenerated reactor 7 according to the change of soda pH value with regard to Row sum-equal matrix, to guarantee that the solution PH in clear liquid collecting pit 7 is stabilized within the scope 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, and remainder is pumped to the pulp storage tank 8 depositing calcium-base absorbing agent.In process, most calcium-base absorbing agent only lives through and once sprays desulfurization, or the spray desulfurization that cycle-index is little, ensure that calcium alkali concn higher in calcium-base absorbing agent and lower calcium sulfite concentration.
According to the consumption of calcium-base absorbing agent and the change of pH value, constantly in pulp storage tank 8, supplement fresh calcium-base absorbing agent and fresh water (FW), the calcium-base absorbing agent in pulp storage tank 8 is pumped to spray system 3 and carries out desulfurization.The pH value that calcium-base absorbing agent is higher is conducive to the removal efficiency improving sulfur dioxide, and in operation, PH general control is within the scope of 5.5-6.5
In regenerated reactor 7, the alkaline reaction after calcium-base absorbing agent and desulfurization generates regeneration soda and calcium sulfite precipitation.Regeneration soda is pumped to soda liquid storage tank 1, enters clear liquid collecting pit 4 participate in circulation desulfurization with the fresh soda supplemented into and fresh water (FW) after mixing.Gypsum is produced through techniques such as subsequent oxidation dehydrations after the calcium sulfite precipitation generated is drawn out of.
Above; be only preferred embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should define with claim is as the criterion.
Claims (7)
1. a sodalime double alkali method double circulation desulphurization technique, it is characterized in that, comprise and flue gas is inputted in reaction tower, carry out the desulfurization of soda section, the desulfurization of calcium method section successively, be specially: first utilize soda to carry out desulfurization to the sulfur dioxide in flue gas, then the flue gas utilization calcium-base absorbing agent after sodium alkali desulfurization is carried out desulfurization, the flue gas after calcium-based desulfurization is discharged through demister;
The soda clear liquid input soda regenerated reactor obtained after collecting the desulfurization of soda section, the calcium-based slurries obtained after collecting the desulfurization of calcium method section 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, is characterized in that, also comprises and the calcium sulfite precipitation in soda regenerated reactor is carried out being separated, carrying out being oxidized the gypsum that processed technique obtains industrial use.
3. sodalime double alkali method double circulation desulphurization technique according to claim 1, is characterized in that, described soda is NaOH and/or sodium carbonate.
4. sodalime double alkali method double circulation desulphurization technique according to claim 1, is characterized in that, described 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, is characterized in that, the pH value of the slurries in described calcium method absorption system is 5.5 to 6.5.
6. a sodalime double alkali method double circulation desulphurization system, it is characterized in that, comprise a reaction tower, soda regenerated reactor and soda liquid storage tank, calcium-base absorbing agent liquid storage tank, be provided with calcium method desulfurizer, the sodium alkali desulfurizer of upper and lower layout in described reaction tower, wherein
Described calcium method desulfurizer comprises slurries collecting pit, is arranged on above described slurries collecting pit, the calcium method desulfurization spray equipment be communicated with described calcium-base absorbing agent liquid storage tank, and described soda collecting pit is communicated with soda regenerated reactor by slurries conveyance conduit;
Described sodium alkali desulfurizer comprises clear liquid collecting pit, is arranged on above described clear liquid collecting pit, the sodium alkali desulfurization spray equipment be communicated with described soda liquid storage tank, and described soda collecting pit is communicated with soda regenerated reactor by clear liquid conveyance conduit;
Be provided with exhanst gas outlet above described reaction tower, described smoke outlet is provided with demister, and described demister is arranged on the top of calcium method desulfurization spray equipment;
Flue gas is inputted in reaction tower, in described sodium alkali desulfurizer, utilize soda to carry out desulfurization to the sulfur dioxide in flue gas, the soda clear liquid input soda regenerated reactor obtained after desulfurization, then flue gas enters described calcium method desulfurizer and utilizes calcium-base absorbing agent to carry out desulfurization, the calcium-based slurries obtained after collecting desulfurization partly or entirely inputs soda regenerated reactor and carries out soda regeneration, and the flue gas after calcium-based desulfurization is discharged through demister.
7. sodalime double alkali method double circulation desulphurization system according to claim 6, is characterized in that, also comprises and the calcium sulfite precipitation in soda regenerated reactor is carried out being separated, carrying out being oxidized the gypsum that processed obtains industrial use.
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| 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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