CN105413399A - Simultaneous desulphurization and denitration system and process thereof - Google Patents
Simultaneous desulphurization and denitration system and process thereof Download PDFInfo
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- CN105413399A CN105413399A CN201510848858.8A CN201510848858A CN105413399A CN 105413399 A CN105413399 A CN 105413399A CN 201510848858 A CN201510848858 A CN 201510848858A CN 105413399 A CN105413399 A CN 105413399A
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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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
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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
- B01D53/14—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 by absorption
- B01D53/1425—Regeneration of liquid absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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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 simultaneous desulphurization and denitration system and a process thereof and belongs to the technical field of desulphurization and denitration. The simultaneous desulphurization and denitration system is a system capable of simultaneously performing desulphurization and denitration on flue gas and can effectively solve the problem that desulphurization and denitration requires two sets of separate devices for removal. The simultaneous desulphurization and denitration system utilizes the same device to simultaneously perform desulphurization and denitration treatment on flue gas by performing flue gas desulphurization and denitration in the same absorption tower device, can simplify equipment, scale, process control and the like and meanwhile can save the operating cost. In addition, the system can also utilize condensate by-products produced during desulphurization treatment to directly regenerate the denitration pregnant solution produced during denitration treatment. On the one hand, the transfer, storage and other problems of corresponding byproduct products are decreased, and on the other hand, the efficiency of flue gas treatment is improved and the cost is saved through effective combination of the desulphurization and denitration treatment.
Description
Technical field
The present invention relates to desulphurization and denitration technical field, the system of desulphurization and denitration and technique thereof the while of particularly relating to a kind of.
Background technology
At present, at the technical elements of flue gas desulfurization, denitration, the technology of domestic and international comparative maturity uses multisystem to remove SO respectively
2and NO
x, namely come by the independent reactor of two covers, the series of problems such as so just bring equipment needed thereby complexity, larger, technology controlling and process is loaded down with trivial details and operating cost is high, therefore exploitation can simultaneously to SO
2and NO
xthe technology carrying out removing must become the new trend of future development.
In the research and development of flue gas desulfurization technique, development is comparatively rapid at present.According to the state of desulfurizing byproduct and the form of sweetening process, flue gas desulfurization technique can be divided into wet method, semidry method and dry method substantially, wherein wet method comprises again limestone-gypsum method, ionic liquid round-robin method, ammoniacal ammonium sulphate method, magnesium processes, Dual alkali, slag method etc.Ionic liquid in ionic liquid round-robin method is based on organic cation and inorganic anion, adds the aqueous solution of a small amount of activator, antioxidant and corrosion inhibiter composition simultaneously, can not produce secondary pollution in use procedure.Ionic liquid absorbs SO at normal temperatures
2, at high temperature, as when 105 ~ 110 DEG C by the SO in ionic liquid
2born again, thus reach the SO removed with in recovered flue gas
2object.Ionic liquid is called as " green can design solvent ", good absorbing effect, and purification efficiency is high, and accommodation is wide, and byproduct is high concentration H
2sO
4, used heat can utilize.Ionic liquid round-robin method sulfur removal technology all has application in flue gas of sintering machine, means of flue gas desulfurization of power plant and chemical plant flue gas desulfurization.In sulfuric acid tail gas improvement, ionic liquid round-robin method can by SO
2concentration is from 10000mg/Nm
3drop to 200mg/Nm
3below, its significant desulfurization effect.
In the research and development of gas denitrifying technology, the mainly selective catalytic reduction (SCR) that current application is more and comparatively ripe and SNCR method (SNCR), but the above temperature requirement of two kinds of techniques to flue gas is higher, usual > 300 DEG C, is not suitable for the denitration process of low-temperature flue gas.Low temperature wet method denitration technology mainly comprises oxidative absorption method, Absorption via Chemical Complexation, reducing process etc.Over nearly 20 years, in view of the high-selenium corn efficiency of wet process complex denitration, the U.S., Japan and the research and development being always devoted to this technology such as European, affecting wet process complex denitration, to apply topmost problem be recycling of absorbing liquid, the method of absorbing liquid circular regeneration mainly contains bioanalysis, chemical method, electrolysis etc., wherein adds reducing agent regenerable absorbent liquid with chemical method and is most widely used.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of system simultaneously carrying out desulphurization and denitration to flue gas, the effective problem solving desulphurization and denitration and need employing two to overlap independent equipment to carry out removing.
The technical solution adopted for the present invention to solve the technical problems is: the system of desulphurization and denitration simultaneously, comprises,
Absorption tower, gas approach is provided with bottom absorption tower, top, absorption tower is provided with exhanst gas outlet, desulfurization section and denitration section is provided with between gas approach to exhanst gas outlet, and desulfurization section is positioned at below denitration section, the upper end of described desulfurization section is doctor solution lean solution entrance, and its lower end is the outlet of doctor solution rich solution; The upper end of described denitration section is denitration liquid lean solution entrance, and its lower end is the outlet of denitration liquid rich solution;
Desulfurization regeneration tower, described desulfurization regeneration tower comprises superposed doctor solution rich solution entrance, be positioned at the outlet of the doctor solution lean solution of bottom and be positioned at the SO at top
2acid gas exports, described doctor solution rich solution entrance and doctor solution rich solution outlet, and the outlet of doctor solution lean solution is communicated with denitration liquid lean solution entrance;
Cooler, described cooler comprises SO
2acid gas entrance, condensate outlet and SO
2outlet, described SO
2acid gas entrance and SO
2acid gas outlet; SO
2outlet is communicated with downstream acid-producing apparatus;
Denitration liquid regenerative response groove, described denitration liquid regenerative response groove comprises condensate inlet, the outlet of denitration liquid lean solution and denitration liquid rich solution entrance; Described condensate inlet is communicated with condensate outlet, and described denitration liquid lean solution outlet is communicated with denitration liquid lean solution entrance, described denitration liquid rich solution entrance and denitration liquid rich solution outlet;
Doctor solution heat exchanger, described doctor solution rich solution entrance after doctor solution heat exchanger with doctor solution rich solution outlet, doctor solution lean solution outlet be communicated with denitration liquid lean solution entrance after doctor solution heat exchanger.
In addition, the technique of desulphurization and denitration while that the present invention also providing a kind of, the system of desulphurization and denitration while of adopting above-mentioned; First in desulfurization section, by ionic liquid, desulfurization process is carried out to flue gas, secondly in denitration section with passing through Fe
2+the complexing agent that coordination is formed carries out denitration process to flue gas; The sulfur removing pregnant solution formed after desulfurization process is through desulfurization regeneration tower regeneration Posterior circle; Desulfurization regeneration tower is to the SO formed in sulfur removing pregnant solution regenerative process
2acid gas forms condensate liquid after cooler condensation, and described condensate liquid joins in denitration liquid regenerative response groove, and the denitration rich solution formed after denitration process is through denitration liquid regenerative response groove regeneration Posterior circle.
Further: absorb temperature when ionic liquid carries out desulfurization process to flue gas in desulfurization section and control at 40 ~ 60 DEG C, liquid-gas ratio controls at 5 ~ 20L/m
3, the pH of ionic liquid controls 5.0 ~ 6.5, and the concentration of ionic liquid controls at 0.5 ~ 2mol/L.
Further: Fe
2+the complexing agent that coordination is formed absorbs temperature when carrying out denitration process to flue gas in denitration section and controls at 30 ~ 50 DEG C, and liquid-gas ratio controls at 3 ~ 10L/m
3, the pH of complexing agent controls 3 ~ 5, in complexing agent: Fe
2+concentration control at 0.02 ~ 0.1mol/L.
Further: with Fe
2+the material that coordination forms complexing agent is made up of one or more mixing in disodium ethylene diamine tetraacetate (EDTA), nitrilotriacetic acid (NTA), diethylene triamine pentacetic acid (DTPA), glutathione, triethylene tetramine, citric acid, triethanolamine, ethylenediamine, pentanedione, amine oxalic acid, and Fe
2+be 1:0.8 ~ 1:5 with the mol ratio of coordinating species.
Further: the pH entering into the condensate liquid of denitration liquid regenerative response groove from condensate inlet controls at 2.5 ~ 4.5, SO
3 2-content control at 5 ~ 15g/L, temperature controls at 30 ~ 50 DEG C; Mixing speed in denitration liquid regenerative response groove controls at 100 ~ 500rpm.
The invention has the beneficial effects as follows: by being arranged in the equipment of same absorption tower the desulfurization of flue gas and denitration, achieving and utilizing same equipment to carry out desulphurization and denitration process to flue gas simultaneously; Can simplified apparatus, scale and technology controlling and process etc., operating cost can be saved simultaneously; In addition, condensate liquid accessory substance also by producing during desulfurization process, directly the denitration rich solution that denitration process produces is regenerated, save the problem such as transhipment, storage to corresponding accessory substance product on the one hand, on the other hand desulphurization and denitration process is effectively combined, improve fume treatment efficiency, cost-saving.
Accompanying drawing explanation
Fig. 1 is the structural representation of the system of desulphurization and denitration while of inventing described;
Be labeled as in figure: absorption tower 1, gas approach 11, exhanst gas outlet 12, desulfurization section 2, doctor solution lean solution entrance 21, doctor solution rich solution outlet 22, denitration section 3, denitration liquid lean solution entrance 31, denitration liquid rich solution outlet 32, desulfurization regeneration tower 4, doctor solution rich solution entrance 41, doctor solution lean solution outlet 42, SO
2acid gas outlet 43, cooler 5, SO
2acid gas entrance 51, condensate outlet 52, SO
2outlet 53, denitration liquid regenerative response groove 6, condensate inlet 61, denitration liquid lean solution outlet 62, denitration liquid rich solution entrance 63, doctor solution heat exchanger 7.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is further described.
As shown in Figure 1, while of the present invention, the system of desulphurization and denitration, comprises,
Absorption tower 1, gas approach 11 is provided with bottom absorption tower, top, absorption tower is provided with exhanst gas outlet 12, desulfurization section 2 and denitration section 3 is provided with between gas approach 11 to exhanst gas outlet 12, and desulfurization section 2 is positioned at below denitration section 3, the upper end of described desulfurization section 2 is doctor solution lean solution entrance 21, and its lower end is doctor solution rich solution outlet 22; The upper end of described denitration section 3 is denitration liquid lean solution entrance 31, and its lower end is denitration liquid rich solution outlet 32;
Desulfurization regeneration tower 4, described desulfurization regeneration tower 4 comprises superposed doctor solution rich solution entrance 41, be positioned at the doctor solution lean solution of bottom outlet 42 and be positioned at the SO at top
2acid gas outlet 43, described doctor solution rich solution entrance 41 exports 22 with doctor solution rich solution and is communicated with, and doctor solution lean solution outlet 42 is communicated with denitration liquid lean solution entrance 31;
Cooler 5, described cooler 5 comprises SO
2acid gas entrance 51, condensate outlet 52 and SO
2outlet 53, described SO
2acid gas entrance 51 and SO
2acid gas outlet 43 is communicated with; SO
2outlet 53 is communicated with downstream acid-producing apparatus;
Denitration liquid regenerative response groove 6, described denitration liquid regenerative response groove 6 comprises condensate inlet 61, denitration liquid lean solution outlet 62 and denitration liquid rich solution entrance 63; Described condensate inlet 61 is communicated with condensate outlet 52, and described denitration liquid lean solution outlet 62 is communicated with denitration liquid lean solution entrance 31, and described denitration liquid rich solution entrance 63 exports 32 with denitration liquid rich solution and is communicated with;
Doctor solution heat exchanger 7, described doctor solution rich solution entrance 41 exports 22 with doctor solution rich solution and is communicated with after doctor solution heat exchanger 7, and doctor solution lean solution outlet 42 is communicated with denitration liquid lean solution entrance 31 after doctor solution heat exchanger 7.
Wherein, be communicated with by pipeline between corresponding entrance and exit, and then realize the transport of gas or liquid; Certainly, on part pipeline, may also need to provide certain power to realize conveying operations, for this reason, often need on corresponding pipeline, arrange the equipment for providing transportation power for liquid or gas etc. such as pump, blower fan or compressor.
In the present invention, undertaken by desulfurization process and denitration process are arranged in same absorption tower, and before desulfurization process is arranged on denitration process, simultaneously, the accessory substance also will produced in desulfurization processing procedure, both condensate liquid was directly delivered in denitration liquid regenerative response groove 6, owing to being dissolved with a certain amount of SO in condensate liquid
2, therefore there is SO in condensate liquid
3 2-and HSO
3 1-plasma, can realize carrying out regeneration process to the denitration rich solution produced in denitration processing procedure, on the one hand, effectively make use of produce in desulfurization processing procedure accessory substance, saved the problem such as transhipment, storage to corresponding accessory substance product; On the other hand, desulphurization and denitration process is effectively combined, improve fume treatment efficiency, cost-saving.
In addition, the present invention also provide a kind of adopt system of the present invention to realize while the technique of desulphurization and denitration, first desulfurization section 2 in, by ionic liquid, desulfurization process is carried out to flue gas, next in denitration section 3 with passing through Fe
2+the complexing agent that coordination is formed carries out denitration process to flue gas; The sulfur removing pregnant solution formed after desulfurization process regenerates Posterior circle through desulfurization regeneration tower 4; The SO formed in desulfurization regeneration tower 4 pairs of sulfur removing pregnant solution regenerative processes
2acid gas forms condensate liquid after cooler 5 condensation, and described condensate liquid joins in denitration liquid regenerative response groove 6, and the denitration rich solution formed after denitration process regenerates Posterior circle through denitration liquid regenerative response groove 6.
Embodiment 1:
Containing SO in flue gas
2concentration is 500 ~ 800ppm, NO
xconcentration is 200 ~ 300ppm, oxygen concentration 8%, and ionic liquid concentration is 0.5mol/L, Fe
2+complexing agent is formed, wherein Fe with disodium ethylene diamine tetraacetate (EDTA) coordination
2+concentration be 0.02mol/L; Absorbing temperature during desulfurization process is 50 DEG C, and liquid-gas ratio is 10L/m
3, the pH of ionic liquid is 6; Absorbing temperature during denitration process is 45 DEG C, and liquid-gas ratio is 5L/m
3, the pH of complexing agent is 4; PH to the condensate liquid of denitration liquid regenerative response groove is 4, SO
3 2-content is 5g/L, and temperature is 50 DEG C; Mixing speed in denitration liquid regenerative response groove is 200rpm.Result is: SO
2removal efficiency can reach 97 ~ 99%, NO
xremoval efficiency can reach 85 ~ 90%.
Embodiment 2:
Containing SO in flue gas
2concentration is 1000 ~ 1500ppm, NO
xconcentration is 300 ~ 500ppm, oxygen concentration 14%, and ionic liquid concentration is 1mol/L, Fe
2+complexing agent is formed, wherein Fe with nitrilotriacetic acid (NTA) coordination
2+concentration be 0.05mol/L; Absorbing temperature during desulfurization process is 50 DEG C, and liquid-gas ratio is 15L/m
3, the pH of ionic liquid is 5.5; Absorbing temperature during denitration process is 45 DEG C, and liquid-gas ratio is 7L/m
3, the pH of complexing agent is 4; PH to the condensate liquid of denitration liquid regenerative response groove is 4, SO
3 2-content is 10g/L, and temperature is 50 DEG C; Mixing speed in denitration liquid regenerative response groove is 300rpm.Result is: SO
2removal efficiency can reach 95 ~ 97%, NO
xremoval efficiency can reach 75 ~ 80%.
Embodiment 3:
Containing SO in flue gas
2concentration is 1500 ~ 2000ppm, NO
xconcentration is 800 ~ 1000ppm, oxygen concentration 8%, and ionic liquid concentration is 1.5mol/L, Fe
2+complexing agent is formed, wherein Fe with diethylene triamine pentacetic acid (DTPA) coordination
2+concentration be 0.1mol/L, during desulfurization process absorb temperature be 45 DEG C, liquid-gas ratio is 15L/m
3, the pH of ionic liquid is 5.5; Absorbing temperature during denitration process is 40 DEG C, and liquid-gas ratio is 10L/m
3, the pH of complexing agent is 4.5; PH to the condensate liquid of denitration liquid regenerative response groove is 4.5, SO
3 2-content is 15g/L, and temperature is 45 DEG C; Mixing speed in denitration liquid regenerative response groove is 500rpm.Result is: SO
2removal efficiency can reach 93 ~ 96%, NO
xremoval efficiency can reach 70 ~ 75%.
Embodiment 4:
Containing SO in flue gas
2concentration is 2000 ~ 3000ppm, NO
xconcentration is 800 ~ 1000ppm, oxygen concentration 14%, and ionic liquid concentration is 2mol/L, Fe
2+complexing agent is formed, wherein Fe with disodium ethylene diamine tetraacetate (EDTA) and nitrilotriacetic acid (NTA) coordination
2+concentration be 0.1mol/L, during desulfurization process absorb temperature be 45 DEG C, liquid-gas ratio is 20L/m
3, the pH of ionic liquid is 5.5; Absorbing temperature during denitration process is 40 DEG C, and liquid-gas ratio is 10L/m
3, the pH of complexing agent is 4.5; PH to the condensate liquid of denitration liquid regenerative response groove is 4.5, SO
3 2-content is 15g/L, and temperature is 45 DEG C; Mixing speed in denitration liquid regenerative response groove is 500rpm.Result is: SO
2removal efficiency can reach 90 ~ 95%, NO
xremoval efficiency can reach 65 ~ 70%.
Claims (6)
1. while, the system of desulphurization and denitration, is characterized in that: comprise,
Absorption tower (1), gas approach (11) is provided with bottom absorption tower, exhanst gas outlet (12) is provided with at top, absorption tower, desulfurization section (2) and denitration section (3) is provided with between gas approach (11) to exhanst gas outlet (12), and desulfurization section (2) is positioned at denitration section (3) below, the upper end of described desulfurization section (2) is doctor solution lean solution entrance (21), and its lower end is doctor solution rich solution outlet (22); The upper end of described denitration section (3) is denitration liquid lean solution entrance (31), and its lower end is denitration liquid rich solution outlet (32);
Desulfurization regeneration tower (4), described desulfurization regeneration tower (4) comprises superposed doctor solution rich solution entrance (41), be positioned at the doctor solution lean solution of bottom outlet (42) and be positioned at the SO at top
2acid gas outlet (43), described doctor solution rich solution entrance (41) exports (22) and is communicated with doctor solution rich solution, doctor solution lean solution outlet (42) is communicated with denitration liquid lean solution entrance (31);
Cooler (5), described cooler (5) comprises SO
2acid gas entrance (51), condensate outlet (52) and SO
2outlet (53), described SO
2acid gas entrance (51) and SO
2acid gas outlet (43) is communicated with; SO
2outlet (53) is communicated with downstream acid-producing apparatus;
Denitration liquid regenerative response groove (6), described denitration liquid regenerative response groove (6) comprises condensate inlet (61), the outlet of denitration liquid lean solution (62) and denitration liquid rich solution entrance (63); Described condensate inlet (61) is communicated with condensate outlet (52), described denitration liquid lean solution outlet (62) is communicated with denitration liquid lean solution entrance (31), and described denitration liquid rich solution entrance (63) exports (32) and is communicated with denitration liquid rich solution;
Doctor solution heat exchanger (7), described doctor solution rich solution entrance (41) exports (22) and is communicated with after doctor solution heat exchanger (7) with doctor solution rich solution, doctor solution lean solution outlet (42) is communicated with denitration liquid lean solution entrance (31) after doctor solution heat exchanger (7).
2. while, the technique of desulphurization and denitration, is characterized in that: the system of desulphurization and denitration while of adopting according to claim 1; First in desulfurization section (2), by ionic liquid, desulfurization process is carried out to flue gas, secondly in denitration section (3) with passing through Fe
2+the complexing agent that coordination is formed carries out denitration process to flue gas; The sulfur removing pregnant solution formed after desulfurization process is through desulfurization regeneration tower (4) regeneration Posterior circle; Desulfurization regeneration tower (4) is to the SO formed in sulfur removing pregnant solution regenerative process
2acid gas forms condensate liquid after cooler (5) condensation, and described condensate liquid joins in denitration liquid regenerative response groove (6), and the denitration rich solution formed after denitration process is through denitration liquid regenerative response groove (6) regeneration Posterior circle.
3. the technique of desulphurization and denitration simultaneously as claimed in claim 2, is characterized in that: absorb temperature when ionic liquid carries out desulfurization process to flue gas in desulfurization section (2) and control at 40 ~ 60 DEG C, liquid-gas ratio controls at 5 ~ 20L/m
3, the pH of ionic liquid controls 5.0 ~ 6.5, and the valid density of ionic liquid controls at 0.5 ~ 2mol/L.
4. the technique of desulphurization and denitration simultaneously as claimed in claim 2, is characterized in that: Fe
2+the complexing agent that coordination is formed absorbs temperature when carrying out denitration process to flue gas in denitration section (3) and controls at 30 ~ 50 DEG C, and liquid-gas ratio controls at 3 ~ 10L/m
3, the pH of complexing agent controls 3 ~ 5, Fe in complexing agent
2+concentration control at 0.02 ~ 0.1mol/L.
5. the technique of desulphurization and denitration simultaneously as claimed in claim 2, is characterized in that: with Fe
2+the material that coordination forms complexing agent is made up of one or more mixing in disodium ethylene diamine tetraacetate (EDTA), nitrilotriacetic acid (NTA), diethylene triamine pentacetic acid (DTPA), glutathione, triethylene tetramine, citric acid, triethanolamine, ethylenediamine, pentanedione, amine oxalic acid, and Fe
2+be 1:0.8 ~ 1:5 with the mol ratio of coordinating species.
6. the technique of desulphurization and denitration simultaneously as claimed in claim 2, is characterized in that: the pH entering into the condensate liquid of denitration liquid regenerative response groove (6) from condensate inlet (61) controls at 2.5 ~ 4.5, SO
3 2-content control at 5 ~ 15g/L, temperature controls at 30 ~ 50 DEG C; Mixing speed in denitration liquid regenerative response groove (6) controls at 100 ~ 500rpm.
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