CN105413428A - Flue gas desulfurization process adopting organic amine method - Google Patents
Flue gas desulfurization process adopting organic amine method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The invention discloses a flue gas desulfurization process adopting an organic amine method and belongs to the technical field of flue gas desulfurization. The flue gas desulfurization process adopting the organic amine method can ensure a desulfurizing agent recovering effect, improve a SO2 removal effect and reduce SO2 emission concentration. The process comprises the steps of main desulfurization circular treatment, resin desalting treatment and desulfurizing agent recovery circular treatment. In the resin desalting treatment process, desalting output liquid discharged firstly and first washing output liquid discharged subsequently are mixed in a mixing tank to obtain mixed liquid, and the mixed liquid is added into the desulfurizing agent recovery circular treatment after being subjected to thermal refining. By analyzing the characteristic of an existing flue gas desulfurization process adopting the organic amine method, it is creatively put forward that the desulfurized solution subjected to resin desalting treatment and the first washing output liquid are mixed, and the mixed liquid formed through mixing is added into a recovery section of an adsorption tower after being subjected to thermal refining, and it is ensured that SO2 can be removed further while the desulfurizing agent is recovered; the emission concentration of SO2 in flue gas meets a new emission standard.
Description
Technical field
The present invention relates to flue gas desulfurization technique field, particularly relate to a kind of amine process flue gas desulfurization technique.
Background technology
Amine process flue gas desulfurization technique is a kind of desulfur technology that application is comparatively common at present, and it take organic amine as desulfurizing agent, the SO in cyclic absorption flue gas
2and make sulfuric acid, be a kind of flue gas desulfurization technique of real efficient green, the sinter fume of Duo Jia iron and steel enterprise at home at present has application.
Accompanying drawing 1 is amine process flue gas desulfurization process figure in prior art, comprises main desulphurization circulating process 1, resin desalting processing 2 and desulfurizing agent and reclaims circular treatment 3 three part; Its concrete technology flow process is as follows:
In main desulphurization circulating process 1, sulfur removing pregnant solution in rich solution groove 14, become after Analytic Tower resolves 13 and resolve lean solution 11, parsing lean solution 11 is diverted to by major part after heat exchanger 12 heat exchange the absorber portion being positioned at absorption tower hypomere and carries out absorber portion desulfurization 15, carry out smoke absorption desulfurization, the sulfur removing pregnant solution after Absorption Desulfurization is got back in rich solution groove 14.
Resolve lean solution 11 to be diverted in resin desalting processing 2 by small part after heat exchanger 12 heat exchange and to carry out resin desalination 21 and process, remove the thermal-stable salt of accumulation, carrying out in resin desalination 21 process, regenerated from washing need be carried out with soft water and alkali lye to resin successively, the desulfurizing agent carried secretly with eluted resin and make resin recover desalting ability; Therefore carrying out in resin desalination 21 process, producing desalination fluid 22, first washing fluid 23, alkali cleaning fluid 24 and the second washing fluid successively; Wherein, desalination fluid 22 and the first washing fluid 23 flow back in main desulphurization circulating process 1 and continue to use, and store separately after alkali cleaning fluid 24 and the second washing fluid are then mixed to form washings 26.
It is arrange exhausting section at absorption tower epimere that desulfurizing agent reclaims circular treatment 3, by recovery pump 31 and accumulator tank 32, realizes the desulfurizing agent that recovered flue gas is carried secretly; And then reduce the consumption of desulfurizing agent.Desulfurizing agent reclaims in circular treatment 3, and reclaiming the solution after desulfurizing agent 33 actual through exhausting section is sulfur removing pregnant solution, and its major part is shunted back in accumulator tank 32 and realized circulation, and small part then branches in the rich solution groove 14 in main desulphurization circulating process 1.PH operationally in exhausting section is about 2 ~ 3, therefore almost can only realize the recovery of desulfurizing agent, not have desulphurizing ability completely.
But the process of above-mentioned existing amine process flue gas desulfurization technique, its desulfurized effect is unsatisfactory, to the SO in flue gas
2only can realize removing in main desulphurization circulating process 1, and cannot realize SO further in desulfurizing agent recovery circular treatment 3
2remove.
In recent years, along with government department is to the increasing of environmental protection dynamics, also more and more higher to the standard of fume emission, as " steel sintering, the pelletizing industrial air pollution thing discharge standard " of up-to-date promulgation, started to perform from 1 day January in 2015, require SO
2concentration of emission is lower than 200mg/m
3, discharge standard is before this then 600mg/m
3.Therefore cause most of organic amine desulfurizer of having put into operation owing to being by former old discharge standard design-build when it designs, therefore cannot meet new discharge standard, cause the desulphurizing ability of desulfurizer not enough; Often need integral replacing desulphurization plant, or carry out larger device upgrade, cost must be caused to increase; In addition, the flow of sinter fume and SO
2fluctuation of concentration is comparatively large, and the modification scope of amine process flue gas desulphurization system desulfurization section is limited, easily causes the period of desulfurization to exceed discharge standard.
According to the process characteristic of organic amine flue gas desulfurization, as long as make the exhausting section on absorption tower, namely make desulfurizing agent reclaim circular treatment 3 and possess certain desulphurizing ability, can after main desulphurization circulating process 1, to SO
2realize further desulfurization, and then make SO
2reach New emission standard.And make exhausting section possess the fairly simple effective way of certain desulphurizing ability exactly directly to adding NaOH in Ethylene recov, but there are a large amount of NaSO that alkali lye consumption is large and generate in the method
4need deviate from etc. problem.Another easy way is exactly directly to adding desulfurization lean solution in exhausting section, but the method can cause desulfurizing agent to carry loss secretly greatly, and exhausting section forfeiture is to problems such as the recovering effects of desulfurizing agent.
Summary of the invention
The technical problem that the present invention solves is to provide one and can ensures desulfurizing agent recovering effect, can improve SO again
2removal effect, reduces SO
2the amine process flue gas desulfurization technique of concentration of emission.
The technical solution adopted for the present invention to solve the technical problems is: amine process flue gas desulfurization technique, comprise main desulphurization circulating process, resin desalting processing and desulfurizing agent and reclaim circular treatment, the desalination fluid of first discharging in resin desalting processing process and the first washing fluid of discharging afterwards mix and obtain mixed liquor in mixing channel, and mixed liquor joins desulfurizing agent and reclaims in circular treatment after modifier treatment.
Further: in modifier treatment process, the pH regulating mixed liquor is 5.5 ~ 7; And controlling organic amine concentration in mixed liquor is 10 ~ 20g/L, SO
4 2-concentration is 10 ~ 40g/L, SO
3 2-concentration is 1 ~ 5g/L.
Further: described desalination fluid and first is washed fluid and is mixed to get mixed liquor according to the ratio that volume ratio is 0.3 ~ 0.8 ﹕ 1.
Further: the pH of desalination fluid controls 6.5 ~ 7.5, and in desalination fluid, organic amine concentration controls at 40 ~ 50g/L, SO
4 2-concentration controls at 20 ~ 50g/L, SO
3 2-concentration controls at 1 ~ 5g/L.
Further: the pH of the first washing fluid controls 5 ~ 7, in the first washing fluid, organic amine concentration controls at 0 ~ 5g/L, SO
4 2-concentration controls at 0 ~ 10g/L, SO
3 2-concentration controls at 0 ~ 3g/L.
Further: mixed liquor joins desulfurizing agent and reclaims on the outlet conduit of recovery pump in circular treatment, enters the exhausting section on absorption tower in after mixing with the circulation fluid in recovery pump outlet conduit.
Further: the pH of the mixed solution of circulation fluid in mixed liquor and recovery pump outlet conduit controls 4.5 ~ 7, and in this solution, organic amine concentration controls at 10 ~ 30g/L, SO
4 2-concentration controls at 10 ~ 60g/L, SO
3 2-concentration controls at 1 ~ 8g/L.
Further: reclaim in circular treatment (3) at desulfurizing agent, the temperature being positioned at the exhausting section on absorption tower controls at 35 ~ 50 DEG C, and liquid-gas ratio controls at 0.5 ~ 4L/m
3.
Further: the parsing lean solution in main desulphurization circulating process after Analytic Tower is resolved by heat exchanger heat exchange after to flow into amount in resin desalting processing with the volume ratio of the amount flowing into absorber portion desulfurization be 0.5 ~ 2 ﹕ 20.
Further: mixed liquor joins desulfurizing agent and reclaims amount in circular treatment and desulfurizing agent to reclaim the amount be drained in main desulphurization circulating process after circular treatment consistent.
The invention has the beneficial effects as follows: by the analysis to existing amine process flue gas desulfurization technique feature, the present invention proposes the desulfuration solution after by resin desalting processing innovatively, the first washing fluid mixes, and by the mixed liquor be mixed to form again through joining in the exhausting section on absorption tower after modifier treatment, desulfurizing agent can be made to reclaim circular treatment and to play SO in flue gas while carrying out desulfurizing agent recovery
2remove further; Further, by the modulation treatment to mixed liquor, the SO of mixed liquor for low concentration can be improved
2remove ability; While guaranteeing to reclaim desulfurizing agent, SO can be reduced further
2concentration of emission; Make original desulfurizer, can SO be made without the need to integral replacing or larger upgrading
2concentration of emission meet new discharge standard.Further, after adopting technique of the present invention, all can realize SO because main desulphurization circulating process and desulfurizing agent reclaim in circular treatment
2remove, therefore its adjustable range is larger, more can adapt to flow and the SO of flue gas
2concentration larger fluctuation, guarantees desulfurization emission compliance.
Accompanying drawing explanation
Fig. 1 is amine process flue gas desulfurization process figure in prior art;
Fig. 2 is amine process flue gas desulfurization process figure of the present invention;
Be labeled as in figure: main desulphurization circulating process 1, parsing lean solution 11, heat exchanger 12, Analytic Tower parsing 13, rich solution groove 14, absorber portion desulfurization 15, resin desalting processing 2, resin desalination 21, desalination fluid 22, first wash fluid 23, alkali cleaning fluid 24, second washing fluid 25, washings 26, mixing channel 27, desulfurizing agent recovery circular treatment 3, recovery pump 31, accumulator tank 32, exhausting section recovery desulfurization 33.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is further described.
As shown in Figure 2, amine process flue gas desulfurization technique of the present invention, comprise main desulphurization circulating process 1, resin desalting processing 2 and desulfurizing agent and reclaim circular treatment 3, the desalination fluid 22 of first discharging in resin desalting processing 2 process and the first washing fluid 23 of discharging afterwards mix and obtain mixed liquor in mixing channel 27, and mixed liquor joins desulfurizing agent and reclaims in circular treatment 3 after modifier treatment.
The present invention arranges a mixing channel 27 by increasing in resin desalting processing 2 process, the desalination fluid 22 of generation and the first washing fluid 23 are successively discharged in mixing channel 27 simultaneously and mix, and modulation treatment is carried out to mixed mixed liquor, to make the mixed liquor after modulation can for the SO of low concentration in flue gas
2remove, the recovery to desulfurizing agent can be realized again.As for concrete modulation processing method, can adopt and regulate by adding acid, alkali or new desulfurizing agent etc.
Meet above-mentioned requirements in order to what make that the mixed liquor after modulating can be optimum, the mixed liquor preferably after modulation has following character: the pH of mixed liquor is 5.5 ~ 7; And controlling organic amine concentration in mixed liquor is 10 ~ 20g/L, SO
4 2-concentration is 10 ~ 40g/L, SO
3 2-concentration is 1 ~ 5g/L.
More specifically, desalination fluid 22 and first is washed the ratio that fluid 23 can be 0.3 ~ 0.8 ﹕ 1 according to volume ratio and is carried out being mixed to get mixed liquor.The mixed liquor obtained like this, the modulation treatment after being more convenient for.Further, on the basis of aforementioned proportion, can limit the character of desalination fluid 22 and the first washing fluid 23 further, as controlled 6.5 ~ 7.5 by the pH of desalination fluid 22, in desalination fluid 22, organic amine concentration controls at 40 ~ 50g/L, SO
4 2-concentration controls at 20 ~ 50g/L, SO
3 2-concentration controls at 1 ~ 5g/L; Control 5 ~ 7 by the pH of the first washing fluid 23, in the first washing fluid 23, organic amine concentration controls at 0 ~ 5g/L, SO
4 2-concentration controls at 0 ~ 10g/L, SO
3 2-concentration controls at 0 ~ 3g/L.By such control, by desalination fluid 22 and the mixed mixed liquor obtained of the first washing fluid 23, itself directly can use or can instructions for use be met after only needing simple modifier treatment.The difficulty of the modifier treatment after can simplifying.
In addition, the mixed liquor after modified can directly join in the exhausting section on absorption tower, directly carries out contacting with flue gas absorbing SO
2with recovery absorbent; As joined on the outlet conduit of recovery pump 31 in desulfurizing agent recovery circular treatment 3 by mixed liquor, enter in the exhausting section on absorption tower after mixing with the circulation fluid in recovery pump outlet conduit.More specifically, also can control mixed liquor and mix according to certain ratio with the circulation fluid in recovery pump outlet conduit, and the pH of mixed solution is controlled 4.5 ~ 7, and in this solution, organic amine concentration controls at 10 ~ 30g/L, SO
4 2-concentration controls at 10 ~ 60g/L, SO
3 2-concentration controls at 1 ~ 8g/L; And then can in exhausting section, have optimum desulfurized effect to flue gas and reclaim the effect of desulfurizing agent after guaranteeing the solution that mixes.
In addition, owing to reclaiming in circular treatment 3 at desulfurizing agent in the present invention, process needs to realize the recovery to desulfurizing agent, also needs the SO in flue gas
2realize further removing, therefore, also need corresponding adjustment for the operational parameter control in absorber portion, the present invention is preferably as follows controling parameters: the temperature in exhausting section controls at 35 ~ 50 DEG C, and liquid-gas ratio controls at 0.5 ~ 4L/m
3.
It is in addition, adjustable that in main desulphurization circulating process 1, resolve the parsing lean solution 11 after 13 by flowing into amount in resin desalting processing 2 after heat exchanger 12 heat exchange with the volume ratio of the amount flowing into absorber portion desulfurization 15 through Analytic Tower be 0.5 ~ 2 ﹕ 20.The normal process of main desulphurization circulating process 1 can be ensured on the one hand, meet on the other hand in exhausting section SO
2remove and desulfurizing agent reclaim needs.
In addition, in order to ensure that desulfurizing agent reclaims circular treatment 3 and can run by continuous circulation, ensure the stable of its inner loop flow, require that mixed liquor joins desulfurizing agent and reclaims amount in circular treatment 3 and desulfurizing agent to reclaim the amount be drained in main desulphurization circulating process 1 after circular treatment 3 consistent.
Embodiment 1:
Certain steel works sintering flue gas, flue gas flow 600000Nm
3/ h, import SO
2concentration is 5000mg/Nm
3, oxygen concentration 14%, in main desulphurization circulating process 1, in desulfurizing agent, organic amine concentration is 50g/L, and desulfurizing agent internal circulating load is 400m
3/ h, runs by sulfur removal technology shown in Fig. 1, records outlet SO
2concentration is 300 ~ 350mg/Nm3, does not meet new discharge standard.
Embodiment 2:
Certain steel works sintering flue gas, flue gas flow 600000Nm
3/ h, import SO
2concentration is 5000mg/Nm3, oxygen concentration 14%, and in main desulphurization circulating process 1, in desulfurizing agent, organic amine concentration is 50g/L, and desulfurizing agent internal circulating load is 400m
3/ h, run by sulfur removal technology shown in Fig. 2, and after modifier treatment, the pH of mixed liquor controls 5.5, in mixed liquor, organic amine concentration controls at 10g/L, SO
4 2-concentration controls at 20g/L, SO
3 2-concentration controls at 2g/L, records outlet SO
2concentration is 170 ~ 180mg/Nm3, meets new discharge standard.
Embodiment 3:
Certain steel works sintering flue gas, flue gas flow 600000Nm
3/ h, import SO
2concentration is 5000mg/Nm
3, oxygen concentration 14%, in main desulphurization circulating process 1, in desulfurizing agent, organic amine concentration is 50g/L, and desulfurizing agent internal circulating load is 400m
3/ h, run by sulfur removal technology shown in Fig. 2, and after modifier treatment, the pH of mixed liquor controls 6.5, in mixed liquor, organic amine concentration controls at 15g/L, SO
4 2-concentration controls at 30g/L, SO
3 2-concentration controls at 3g/L, outlet SO
2concentration is 80 ~ 90mg/Nm3, meets new discharge standard.
Embodiment 4:
Certain steel works sintering flue gas, flue gas flow 600000Nm
3/ h, import SO
2concentration is 6000mg/Nm3, oxygen concentration 14%, and in main desulphurization circulating process 1, in desulfurizing agent, organic amine concentration is 50g/L, and desulfurizing agent internal circulating load is 400m
3/ h, run by sulfur removal technology shown in Fig. 2, and after modifier treatment, the pH of mixed liquor controls 6.5, in mixed liquor, organic amine concentration controls at 20g/L, SO
4 2-concentration controls at 30g/L, SO
3 2-concentration controls at 3g/L, outlet SO
2concentration is 140 ~ 150mg/Nm3, meets new discharge standard.
Embodiment 5:
Certain steel works sintering flue gas, flue gas flow 650000Nm
3/ h, import SO
2concentration is 6000mg/Nm3, oxygen concentration 14%, and in main desulphurization circulating process 1, in desulfurizing agent, organic amine concentration is 50g/L, and desulfurizing agent internal circulating load is 400m
3/ h, run by sulfur removal technology shown in Fig. 2, and after modifier treatment, the pH of mixed liquor controls 7, in mixed liquor, organic amine concentration controls at 20g/L, SO
4 2-concentration controls at 40g/L, SO
3 2-concentration controls at 5g/L, outlet SO
2concentration is 180 ~ 190mg/Nm3, meets new discharge standard.
Claims (10)
1. amine process flue gas desulfurization technique, comprise main desulphurization circulating process (1), resin desalting processing (2) and desulfurizing agent and reclaim circular treatment (3), it is characterized in that: the desalination fluid (22) of first discharging in resin desalting processing (2) process and the discharge afterwards first washing fluid (23) mix and obtain mixed liquor in mixing channel (27), and mixed liquor joins desulfurizing agent and reclaims in circular treatment (3) after modifier treatment.
2. amine process flue gas desulfurization technique as claimed in claim 1, is characterized in that: in modifier treatment process, and the pH regulating mixed liquor is 5.5 ~ 7; And controlling organic amine concentration in mixed liquor is 10 ~ 20g/L, SO
4 2-concentration is 10 ~ 40g/L, SO
3 2-concentration is 1 ~ 5g/L.
3. amine process flue gas desulfurization technique as claimed in claim 1 or 2, is characterized in that: described desalination fluid (22) and first is washed fluid (23) and is mixed to get mixed liquor according to the ratio that volume ratio is 0.3 ~ 0.8 ﹕ 1.
4. amine process flue gas desulfurization technique as claimed in claim 3, is characterized in that: the pH of desalination fluid (22) controls 6.5 ~ 7.5, and in desalination fluid (22), organic amine concentration controls at 40 ~ 50g/L, SO
4 2-concentration controls at 20 ~ 50g/L, SO
3 2-concentration controls at 1 ~ 5g/L.
5. amine process flue gas desulfurization technique as claimed in claim 3, is characterized in that: the pH of the first washing fluid (23) controls 5 ~ 7, and in the first washing fluid (23), organic amine concentration controls at 0 ~ 5g/L, SO
4 2-concentration controls at 0 ~ 10g/L, SO
3 2-concentration controls at 0 ~ 3g/L.
6. amine process flue gas desulfurization technique as claimed in claim 1, it is characterized in that: mixed liquor joins desulfurizing agent and reclaims on the outlet conduit of recovery pump (31) in circular treatment (3), enters the exhausting section on absorption tower in after mixing with the circulation fluid in recovery pump outlet conduit.
7. amine process flue gas desulfurization technique as claimed in claim 6, is characterized in that: the pH of the mixed solution of circulation fluid in mixed liquor and recovery pump outlet conduit controls 4.5 ~ 7, and in this solution, organic amine concentration controls at 10 ~ 30g/L, SO
4 2-concentration controls at 10 ~ 60g/L, SO
3 2-concentration controls at 1 ~ 8g/L.
8. amine process flue gas desulfurization technique as claimed in claim 1, is characterized in that: reclaim in circular treatment (3) at desulfurizing agent, the temperature being positioned at the exhausting section on absorption tower controls at 35 ~ 50 DEG C, and liquid-gas ratio controls at 0.5 ~ 4L/m
3.
9. amine process flue gas desulfurization technique as claimed in claim 1, is characterized in that: in main desulphurization circulating process (1) through Analytic Tower resolve the parsing lean solution (11) after (13) by heat exchanger (12) heat exchange after to flow into amount in resin desalting processing (2) with the volume ratio of the amount flowing into absorber portion desulfurization (15) be 0.5 ~ 2 ﹕ 20.
10. amine process flue gas desulfurization technique as claimed in claim 1, is characterized in that: mixed liquor joins desulfurizing agent and reclaims amount in circular treatment (3) and desulfurizing agent to reclaim the amount be drained in main desulphurization circulating process (1) after circular treatment (3) consistent.
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| CN106268216A (en) * | 2016-09-08 | 2017-01-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Multifunctional smoke desulphurization system and sulfur method |
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| CN105413428B (en) | 2018-05-04 |
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