CN105413428B - Amine process flue gas desulfurization technique - Google Patents

Amine process flue gas desulfurization technique Download PDF

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Publication number
CN105413428B
CN105413428B CN201510851678.5A CN201510851678A CN105413428B CN 105413428 B CN105413428 B CN 105413428B CN 201510851678 A CN201510851678 A CN 201510851678A CN 105413428 B CN105413428 B CN 105413428B
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concentration
flue gas
desulfurizing agent
gas desulfurization
mixed liquor
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CN105413428A (en
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王建山
黎建明
邱正秋
张小龙
张亦凡
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/80—Organic bases or salts
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention discloses a kind of amine process flue gas desulfurization technique, belong to flue gas desulfurization technique field, there is provided one kind not only can guarantee that desulfurizing agent recovering effect, but also can improve SO2Removal effect, reduces SO2The amine process flue gas desulfurization technique of concentration of emission, including the processing of main desulphurization circulating, resin desalting processing and desulfurizing agent recycling circular treatment, the first water eluate that the desalination first discharged during resin desalting processing goes out liquid and discharges afterwards mixes in mixing channel and obtains mixed liquor, and mixed liquor is added to after modifier treatment in desulfurizing agent recycling circular treatment.The present invention passes through the analysis to existing amine process flue gas desulfurization technique feature, innovatively propose to be mixed the desulfuration solution after resin desalting processing, the first water eluate, and the mixed liquor being mixed to form is added in the exhausting section on absorption tower after conditioned processing again, while ensuring to recycle desulfurizing agent, SO can be further removed2；Make SO in flue gas2Concentration of emission meet new discharge standard.

Description

Amine process flue gas desulfurization technique
Technical field
The present invention relates to flue gas desulfurization technique field, more particularly to a kind of amine process flue gas desulfurization technique.
Background technology
Amine process flue gas desulfurization technique is to apply a kind of relatively conventional desulfurization technology at present, it is using organic amine as desulfurization Agent, the SO in cyclic absorption flue gas2And sulfuric acid is made, it is a kind of flue gas desulfurization technique of really efficient green, at present at home There is application on the sintering flue gas of Duo Jia iron and steel enterprises.
Attached drawing 1 is amine process flue gas desulfurization process figure, including main desulphurization circulating processing 1, resin in the prior art Desalting processing 2 and desulfurizing agent recycling 3 three parts of circular treatment；Its concrete technology flow process is as follows：
In main desulphurization circulating processing 1, the sulfur removing pregnant solution in rich solution groove 14 is poor as parsing after Analytic Tower parsing 13 Liquid 11, parsing lean solution 11 is largely diverted to after being exchanged heat by heat exchanger 12 to be absorbed in the absorber portion of absorption tower hypomere Section desulfurization 15, carries out to smoke absorption desulfurization, and the sulfur removing pregnant solution after Absorption Desulfurization is returned in rich solution groove 14.
Small part, which is diverted in resin desalting processing 2, after parsing lean solution 11 is exchanged heat by heat exchanger 12 carries out resin desalination 21 Processing, removes the thermal-stable salt of accumulation, during resin desalination 21 is carried out, resin need to be carried out with soft water and lye successively Regenerated from washing, with the desulfurizing agent of eluted resin entrainment and makes resin recover desalting ability；Therefore 21 process of resin desalination is being carried out In will be sequentially generated desalination and go out liquid 22, the first water eluate 23,24 and second water eluate of alkali eluate；Wherein, desalination goes out liquid 22 and first water eluate 23 flow back in main desulphurization circulating processing 1 and be continuing with, and 24 and second water eluate of alkali eluate is then Individually stored after being mixed to form washings 26.
Desulfurizing agent recycling circular treatment 3 is to set exhausting section in absorption tower epimere, real by recovery pump 31 and accumulator tank 32 The desulfurizing agent of existing recovered flue gas entrainment；And then reduce the consumption of desulfurizing agent.In desulfurizing agent recycling circular treatment 3, by exhausting section It is sulfur removing pregnant solution that it is actual, which to recycle the solution after desulfurizing agent 33, it, which is largely shunted back, realizes circulation in accumulator tank 32, small part is then Branch in the rich solution groove 14 in main desulphurization circulating processing 1.Operationally the pH in exhausting section is about 2~3, therefore almost can only The recycling of desulfurizing agent is realized, completely without desulphurizing ability.
However, above-mentioned existing amine process flue gas desulfurization technique processing, its desulfurization effect is unsatisfactory, in flue gas SO2It is only capable of realizing removing in main desulphurization circulating processing 1, and can not be further realized pair in desulfurizing agent recycles circular treatment 3 SO2Removing.
In recent years, it is also higher and higher to the standard of flue gas emission with increasing of the government department to environmental protection dynamics, such as Newest promulgation《Steel sintering, pelletizing industrial air pollution thing discharge standard》, since 1 day January in 2015 perform, it is desirable to SO2Concentration of emission is less than 200mg/m3, and discharge standard before this is then 600mg/m3.Therefore the big portion to have put into operation is caused Divide organic amine desulfurizer can not meet new row due to being by pervious old discharge standard design-build when it is designed Standard is put, causes the desulphurizing ability deficiency of desulfurizer；Integral replacing desulphurization plant is generally required, or carries out larger equipment Upgrading, necessarily causes cost to increase；In addition, the flow and SO of sintering flue gas2Fluctuation of concentration is larger, and amine process flue gas desulfurization The modification scope of system desulfurization section is limited, be easy to cause the period of desulfurization and exceeds discharge standard.
According to the process characteristic of organic amine flue gas desulfurization, as long as making the exhausting section on absorption tower, that is, recycle desulfurizing agent Circular treatment 3 possesses certain desulphurizing ability, you can after main desulphurization circulating processing 1, to SO2Realize further desulfurization, And then make SO2Reach New emission standard.And it is exactly straight exhausting section is possessed the fairly simple effective method of certain desulphurizing ability Connect and add NaOH into recovered liquid, but there are a large amount of NaSO that alkali lye consumption is big and generates for this method4The problems such as needing abjection.Separately A kind of outer easy method is exactly the addition desulfurization lean solution directly into exhausting section, but this method can cause desulfurizing agent entrainment loss Greatly, exhausting section loses the problems such as recovering effect to desulfurizing agent.
The content of the invention
The technical problem to be solved by the present invention is to provide one kind not only can guarantee that desulfurizing agent recovering effect, but also can improve SO2Removing Effect, reduces SO2The amine process flue gas desulfurization technique of concentration of emission.
The technical solution adopted by the present invention to solve the technical problems is：Amine process flue gas desulfurization technique, including it is main de- Sulfur cycle processing, resin desalting processing and desulfurizing agent recycling circular treatment, the desalination first discharged during resin desalting processing The the first water eluate for going out liquid and discharging afterwards mixes in mixing channel and obtains mixed liquor, and mixed liquor adds after modifier treatment Enter to desulfurizing agent and recycle in circular treatment.
It is further：During modifier treatment, the pH for adjusting mixed liquor is 5.5~7；And control organic in mixed liquor Amine concentration is 10~20g/L, SO4 2-Concentration is 10~40g/L, SO3 2-Concentration is 1~5g/L.
It is further：The desalination goes out liquid and is mixed with the first water eluate according to the ratio that volume ratio is 0.3~0.8 ﹕ 1 Obtain mixed liquor.
It is further：Desalination goes out the pH controls of liquid 6.5~7.5, desalination go out in liquid organic amine concentration control 40~ 50g/L, SO4 2-Concentration is controlled in 20~50g/L, SO3 2-Concentration is controlled in 1~5g/L.
It is further：The pH of first water eluate controls organic amine concentration in 5~7, first water eluates to control 0 ~5g/L, SO4 2-Concentration is controlled in 0~10g/L, SO3 2-Concentration is controlled in 0~3g/L.
It is further：Mixed liquor is added in desulfurizing agent recycling circular treatment on the outlet conduit of recovery pump, with recycling Enter after circulation fluid mixing in pump discharge pipeline in the exhausting section on absorption tower.
It is further：The pH of mixed liquor and the mixed solution of circulation fluid in recovery pump outlet conduit is controlled 4.5 ~7, and organic amine concentration is controlled in 10~30g/L, SO in the solution4 2-Concentration is controlled in 10~60g/L, SO3 2-Concentration control System is in 1~8g/L.
It is further：In desulfurizing agent recycling circular treatment (3), the temperature control in the exhausting section on absorption tower exists 35~50 DEG C, liquid-gas ratio is controlled in 0.5~4L/m3。
It is further：After parsing lean solution in the processing of main desulphurization circulating after Analytic Tower parses is exchanged heat by heat exchanger The volume ratio of amount of the amount flowed into resin desalting processing with flowing into absorber portion desulfurization is 0.5~2 ﹕ 20.
It is further：After the amount that mixed liquor is added in desulfurizing agent recycling circular treatment recycles circular treatment with desulfurizing agent The amount being drained into main desulphurization circulating processing is consistent.
The beneficial effects of the invention are as follows：Pass through the analysis to existing amine process flue gas desulfurization technique feature, present invention wound It is proposed to be mixed the desulfuration solution after resin desalting processing, the first water eluate to new property, and it is mixed by what is be mixed to form Close liquid to be added in the exhausting section on absorption tower after conditioned processing again, desulfurizing agent recycling circular treatment can be made to carry out desulfurization Agent is played to SO in flue gas while recycling2Further removing；Also, by the modulation treatment to mixed liquor, it can improve mixed Close the SO that liquid is directed to low concentration2Removing ability；While ensuring to recycle desulfurizing agent, SO can be further reduced2Discharge it is dense Degree；So that original desulfurizer, can make SO without integral replacing or larger upgrading2Concentration of emission meet new discharge Standard.Also, using after technique of the present invention, recycled since main desulphurization circulating is handled with desulfurizing agent in circular treatment Realize to SO2Removing, therefore its adjustable range bigger, is suitable for the flow and SO of flue gas2Concentration larger fluctuation, it is ensured that de- Sulphur emissions are up to standard.
Brief description of the drawings
Fig. 1 is amine process flue gas desulfurization process figure in the prior art；
Fig. 2 is amine process flue gas desulfurization process figure of the present invention；
In figure mark for：Main desulphurization circulating processing 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 go out liquid 22, the first water eluate 23, alkali eluate 24, Two water eluates 25, washings 26, mixing channel 27, desulfurizing agent recycling circular treatment 3, recovery pump 31, accumulator tank 32, exhausting section return Receive desulfurization 33.
Embodiment
The present invention is further described with reference to the accompanying drawings and detailed description.
As shown in Fig. 2, amine process flue gas desulfurization technique of the present invention, including main desulphurization circulating processing 1, resin take off Salt treatment 2 and desulfurizing agent recycling circular treatment 3, the desalination first discharged during resin desalting processing 2 go out the heel row of 22 sum of liquid The the first water eluate 23 gone out mixes in mixing channel 27 and obtains mixed liquor, and mixed liquor is added to desulfurization after modifier treatment In agent recycling circular treatment 3.
Increase during resin desalting processing 2 is set a mixing channel 27 by the present invention, while the desalination of generation is gone out liquid 22 and 23 priority of the first water eluate be discharged into mixing channel 27 and mixed, and place is modulated to mixed mixed liquor Reason, so that modulated mixed liquor can be directed to the SO of low concentration in flue gas2Removed, and can realize and desulfurizing agent is returned Receive.As for specific modulation processing method, it can use and be adjusted by adding acid, alkali or new desulfurizing agent etc..
In order to enable it is modulated mixing liquid energy it is optimal meet above-mentioned requirements, preferably modulated mixed liquor have it is as follows Property：The pH of mixed liquor is 5.5~7；And it is 10~20g/L, SO to control organic amine concentration in mixed liquor4 2-Concentration for 10~ 40g/L、SO3 2-Concentration is 1~5g/L.
More specifically, desalination goes out 22 and first water eluate 23 of liquid and can be carried out according to the ratio that volume ratio is 0.3~0.8 ﹕ 1 It is mixed to get mixed liquor.The mixed liquor so obtained, the modulation treatment after being more convenient for.Also, on the basis of aforementioned proportion, Can further limit the property that desalination goes out 22 and first water eluate 23 of liquid, such as desalination is gone out the pH controls of liquid 22 6.5~ 7.5, desalination goes out organic amine concentration in liquid 22 and controls in 40~50g/L, SO4 2-Concentration is controlled in 20~50g/L, SO3 2-Concentration control System is in 1~5g/L；Organic amine concentration in 5~7, first water eluates 23 is controlled to control 0 the pH of first water eluate 23 ~5g/L, SO4 2-Concentration is controlled in 0~10g/L, SO3 2-Concentration is controlled in 0~3g/L.Control in this way, goes out liquid by desalination 22 and 23 mixed obtained mixed liquor of the first water eluate, itself it can be used directly or need only to and is simple quenched It can meet requirement after processing.The difficulty of modifier treatment after can simplifying.
In addition, the mixed liquor after quenched can be added directly into the exhausting section on absorption tower, directly contact suction is carried out with flue gas Receive SO2With recycling absorbent；Such as can mixed liquor be added to desulfurizing agent recycling circular treatment 3 in recovery pump 31 outlet conduit on, Enter after being mixed with the circulation fluid in recovery pump outlet conduit in the exhausting section on absorption tower.More specifically, also controllable mixed liquor Mixed according to a certain percentage with the circulation fluid in recovery pump outlet conduit, and the pH of mixed solution is controlled 4.5 ~7, and organic amine concentration is controlled in 10~30g/L, SO in the solution4 2-Concentration is controlled in 10~60g/L, SO3 2-Concentration control System is in 1~8g/L；And then can have optimal desulfurization effect and recycling to take off flue gas in exhausting section after ensuring the solution of mixing The effect of sulphur agent.
Further, since in the present invention in desulfurizing agent recycles circular treatment 3, processing needs to realize the recycling to desulfurizing agent, Also need to the SO in flue gas2Realize further removing, therefore, be also required to accordingly for the operational parameter control in absorber portion Adjustment, the present invention is preferably as follows control parameter：Temperature control in exhausting section at 35~50 DEG C, liquid-gas ratio control 0.5~ 4L/m3。
In addition, the parsing lean solution 11 adjusted in main desulphurization circulating processing 1 after Analytic Tower parsing 13 passes through heat exchanger The volume ratio of amount of the amount flowed into after 12 heat exchange in resin desalting processing 2 with flowing into absorber portion desulfurization 15 is 0.5~2 ﹕ 20.One side Face can ensure the normal processing of main desulphurization circulating processing 1, on the other hand meet in exhausting section to SO2Removing and desulfurizing agent return The needs of receipts.
In addition, in order to ensure the 3 continuous circular flow of energy of desulfurizing agent recycling circular treatment, ensure the steady of its internal circular flow It is fixed, it is desirable to which that the amount that mixed liquor is added in desulfurizing agent recycling circular treatment 3 is main de- with being drained into after desulfurizing agent recycling circular treatment 3 Amount in sulfur cycle processing 1 is consistent.
Embodiment 1：
Certain steel works sintering flue gas, flue gas flow 600000Nm3/ h, import SO2Concentration is 5000mg/Nm3, oxygen concentration 14%, organic amine concentration is 50g/L in desulfurizing agent in main desulphurization circulating processing 1, and desulfurizing agent internal circulating load is 400m3/ h, by Fig. 1 institutes Show that sulfur removal technology is run, measure outlet SO2Concentration is 300~350mg/Nm3, is unsatisfactory for new discharge standard.
Embodiment 2：
Certain steel works sintering flue gas, flue gas flow 600000Nm3/ h, import SO2Concentration is 5000mg/Nm3, oxygen concentration 14%, organic amine concentration is 50g/L in desulfurizing agent in main desulphurization circulating processing 1, and desulfurizing agent internal circulating load is 400m3/ h, by Fig. 2 institutes Show that sulfur removal technology is run, and the pH of mixed liquor controls organic amine concentration in 5.5, mixed liquor to control in 10g/ after modifier treatment L、SO4 2-Concentration is controlled in 20g/L, SO3 2-Concentration is controlled in 2g/L, measures outlet SO2Concentration is 170~180mg/Nm3, is met New discharge standard.
Embodiment 3：
Certain steel works sintering flue gas, flue gas flow 600000Nm3/ h, import SO2Concentration is 5000mg/Nm3, oxygen concentration 14%, organic amine concentration is 50g/L in desulfurizing agent in main desulphurization circulating processing 1, and desulfurizing agent internal circulating load is 400m3/ h, by Fig. 2 institutes Show that sulfur removal technology is run, and the pH of mixed liquor controls organic amine concentration in 6.5, mixed liquor to control in 15g/ after modifier treatment L, SO4 2-Concentration is controlled in 30g/L, SO3 2-Concentration control is in 3g/L, outlet SO2Concentration is 80~90mg/Nm3, meets new row Put standard.
Embodiment 4：
Certain steel works sintering flue gas, flue gas flow 600000Nm3/ h, import SO2Concentration is 6000mg/Nm3, oxygen concentration 14%, organic amine concentration is 50g/L in desulfurizing agent in main desulphurization circulating processing 1, and desulfurizing agent internal circulating load is 400m3/ h, by Fig. 2 institutes Show that sulfur removal technology is run, and the pH of mixed liquor controls organic amine concentration in 6.5, mixed liquor to control in 20g/ after modifier treatment L, SO4 2-Concentration is controlled in 30g/L, SO3 2-Concentration control is in 3g/L, outlet SO2Concentration is 140~150mg/Nm3, is met new Discharge standard.
Embodiment 5：
Certain steel works sintering flue gas, flue gas flow 650000Nm3/ h, import SO2Concentration is 6000mg/Nm3, oxygen concentration 14%, organic amine concentration is 50g/L in desulfurizing agent in main desulphurization circulating processing 1, and desulfurizing agent internal circulating load is 400m3/ h, by Fig. 2 institutes Show that sulfur removal technology is run, and the pH of mixed liquor controls organic amine concentration in 7, mixed liquor to control in 20g/L after modifier treatment, SO4 2-Concentration is controlled in 40g/L, SO3 2-Concentration control is in 5g/L, outlet SO2Concentration is 180~190mg/Nm3, meets new row Put standard.

Claims (8)

1. amine process flue gas desulfurization technique, including main desulphurization circulating processing (1), resin desalting processing (2) and desulfurizing agent recycling Circular treatment (3), it is characterised in that：The desalination first discharged during resin desalting processing (2) goes out liquid (22) and discharges afterwards The first water eluate (23) mix in the mixing channel (27) and obtain mixed liquor, mixed liquor is added to de- after modifier treatment In sulphur agent recycling circular treatment (3)；Mixed liquor is added to the outlet conduit of recovery pump (31) in desulfurizing agent recycling circular treatment (3) On, enter after being mixed with the circulation fluid in recovery pump outlet conduit in the exhausting section on absorption tower；During modifier treatment, adjust mixed The pH for closing liquid is 5.5~7；And it is 10~20g/L, SO to control organic amine concentration in mixed liquor4 2-Concentration for 10~40g/L, SO3 2-Concentration is 1~5g/L.
2. amine process flue gas desulfurization technique as claimed in claim 1, it is characterised in that：The desalination goes out liquid (22) and first Water eluate (23) is mixed to get mixed liquor according to the ratio that volume ratio is 0.3~0.8 ﹕ 1.
3. amine process flue gas desulfurization technique as claimed in claim 2, it is characterised in that：The pH controls that desalination goes out liquid (22) exist 6.5~7.5, desalination goes out organic amine concentration in liquid (22) and controls in 40~50g/L, SO4 2-Concentration is controlled in 20~50g/L, SO3 2- Concentration is controlled in 1~5g/L.
4. amine process flue gas desulfurization technique as claimed in claim 2, it is characterised in that：The pH controls of first water eluate (23) System organic amine concentration in 5~7, first water eluates (23) is controlled in 0~5g/L, SO4 2-Concentration is controlled in 0~10g/L, SO3 2-Concentration is controlled in 0~3g/L.
5. amine process flue gas desulfurization technique as claimed in claim 1, it is characterised in that：Mixed liquor and recovery pump outlet conduit The pH of the mixed solution of interior circulation fluid is controlled 4.5~7, and organic amine concentration is controlled in 10~30g/L in the solution, SO4 2-Concentration is controlled in 10~60g/L, SO3 2-Concentration is controlled in 1~8g/L.
6. amine process flue gas desulfurization technique as claimed in claim 1, it is characterised in that：Circular treatment is recycled in desulfurizing agent (3) in, at 35~50 DEG C, liquid-gas ratio is controlled in 0.5~4L/m the temperature control in the exhausting section on absorption tower3。
7. amine process flue gas desulfurization technique as claimed in claim 1, it is characterised in that：In main desulphurization circulating handles (1) Parsing lean solution (11) after Analytic Tower parses (13) flows into the amount in resin desalting processing (2) after exchanging heat by heat exchanger (12) The volume ratio of amount with flowing into absorber portion desulfurization (15) is 0.5~2 ﹕ 20.
8. amine process flue gas desulfurization technique as claimed in claim 1, it is characterised in that：Mixed liquor is added to desulfurizing agent recycling Amount in circular treatment (3) is consistent with the amount being drained into after desulfurizing agent recycling circular treatment (3) in main desulphurization circulating processing (1).
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