CN107174931B - High-efficient flue gas processing apparatus of power is regarded as to ethernet - Google Patents
High-efficient flue gas processing apparatus of power is regarded as to ethernet 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
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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
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a high-efficiency flue gas treatment device taking solar energy as power. The treatment tower is sequentially divided into a first treatment section for removing sulfur dioxide in the waste gas, a second treatment section for oxidizing nitric oxide gas in the waste gas and a third treatment section for removing nitric oxide in the waste gas from bottom to top, a first liquid collecting and gas lifting device is arranged between the first treatment section and the second treatment section, and a second liquid collecting and gas lifting device is arranged between the second treatment section and the third treatment section. The second is handled the section and is passed through second circulating pump and oxidant storage tank intercommunication, and this oxidant storage tank forms a closed circulation with the second and handles the section, and the second is handled the section and is equipped with the catalyst additional. The invention has high desulfurization and denitrification efficiency and low operation cost, greatly reduces the usage amount of the oxidant, and has the total desulfurization efficiency of 99.6 percent and the denitrification efficiency of 98.5 percent.
Description
Technical Field
The invention relates to the technical field of flue gas treatment, in particular to a high-efficiency flue gas treatment device taking solar energy as power.
Background
The combustion of fossil fuels and the waste gas containing sulfur oxides and nitrogen oxides generated in some chemical production cause serious harm to the atmospheric environment, and currently, the desulfurization technology and dry, semi-dry, wet and other types commonly adopted for the treatment of atmospheric pollution are inexpert in the aspect of denitration.
The wet flue gas desulfurization technology is the most widely applied desulfurization technology in the world at present, the desulfurization efficiency is high, and the good vapor-liquid mass transfer of the wet scrubber tower is a potential advantage for absorbing nitrogen oxides, so that the development of the wet flue gas desulfurization and denitration integrated process has a good development prospect.
In the aspect of wet denitration, the oxidation absorption denitration technology overcomes some defects of the SCR technology, and becomes a hotspot of research and development. But the existing wet desulphurization and denitration has the defects of high cost and low efficiency.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a solar-powered high-efficiency flue gas treatment device with high desulfurization and denitrification efficiency and low operation cost.
In order to solve the above technical problems, a first aspect of the present invention provides a high efficiency flue gas treatment device using solar energy as power, which includes a treatment tower and a slurry tank, wherein the slurry tank is disposed at the bottom of the treatment tower and is communicated with the treatment tower, the treatment tower is divided into a first treatment section, a second treatment section and a third treatment section from bottom to top in sequence, a first liquid collecting and gas raising device is disposed between the first treatment section and the second treatment section, a second liquid collecting and gas raising device is disposed between the second treatment section and the third treatment section, the first treatment section is provided with a waste gas inlet, the first treatment section is used for removing sulfur dioxide gas in waste gas, the second treatment section is used for oxidizing nitric oxide gas in waste gas to convert the nitric oxide gas into nitrogen dioxide, the third treatment section is used for removing nitrogen oxide in waste gas and discharging the treated gas out of the treatment tower,
the first treatment section and the third treatment section are communicated with the slurry tank through a first circulating pump, the second treatment section is communicated with an oxidant storage tank through a second circulating pump, the oxidant storage tank and the second treatment section form a closed circulation, the second treatment section is additionally provided with a catalyst,
the third treatment section is also communicated with a circulating tank through a first circulating pipeline, the circulating tank is used for collecting the absorption liquid in the third treatment section, a chemical adding device is arranged on the circulating tank, the circulating tank is communicated with the slurry tank through a second circulating pipeline,
the device also comprises a solar power generation unit which is electrically connected with the first circulating pump and the second circulating pump.
Furthermore, a first spraying absorption device is arranged in the first treatment section, a second spraying absorption device is arranged in the second treatment section, a third spraying absorption device is arranged in the third treatment section and comprises a micro-channel absorption device arranged on the upper portion of the second liquid collecting and gas lifting device, a hollow spraying plate is arranged on the micro-channel absorption device, the spraying plate is communicated with an outlet of the first circulating pump through a first spraying pipeline, the first circulating pump pumps the slurry in the slurry tank to the spraying plate through the first spraying pipeline, and the slurry is sprayed into the micro-channel absorption device through the spraying plate.
Further, the catalyst is an immobilized ionic liquid low-temperature denitration catalyst and comprises 1-60% of active component and 40-99% of carrier by weight, wherein the active component is polyether ionic liquid containing Mg or Al ions.
Further, the first spraying absorption device comprises a first spraying pipe and a packing layer, the first spraying pipe is arranged on the upper portion of the packing layer, the first spraying pipe is communicated with an outlet of the first circulating pump through a second spraying pipeline, the first circulating pump pumps the slurry in the slurry tank to the first spraying pipe through the second spraying pipeline, and the slurry is sprayed into the first treatment section through the first spraying pipe.
Further, the waste gas inlet is arranged to form an angle of 10-30 degrees with the horizontal direction.
Furthermore, a demisting device is arranged at the position, close to the waste gas discharge port, of the treatment tower, the demisting device comprises a demister body and an automatic flushing system, and the automatic flushing system comprises spray pipes arranged at the upper part and the lower part of the demister body and an industrial water tank communicated with the spray pipes.
Furthermore, the slurry tank is communicated with an inlet of the first circulating pump through a first suction pipeline, a first branch is divided from the first suction pipeline, one end of the first branch is connected with the first suction pipeline, the other end of the first branch is connected with the circulating tank, a second branch is divided from the first branch and is used for being communicated with a fresh desulfurization slurry preparation tank.
The second aspect of the present invention further provides a multi-stage waste gas treatment method, which utilizes any one of the multi-stage waste gas treatment devices powered by solar energy provided by the first aspect, and specifically includes the following steps:
1) the waste gas to be treated enters a first treatment section, the waste gas to be treated is contacted with a desulfurizing agent in the first treatment section, and the desulfurizing agent absorbs partial sulfur dioxide in the waste gas to be treated to obtain desulfurization slurry;
2) the waste gas treated by the first treatment section enters a second treatment section for liquid phase oxidation and partial absorption, so that nitric oxide in the waste gas is oxidized into nitrogen dioxide;
3) and (3) the waste gas treated by the second treatment section enters a third treatment section, and the oxidized waste gas is contacted with the desulfurization slurry in the step 1) in the third treatment section, and the desulfurization slurry absorbs nitrogen dioxide and the rest sulfur dioxide in the waste gas.
Flue gas from a boiler flue contains a large amount of sulfur dioxide and nitrogen oxides, the nitrogen oxides mainly comprise nitrogen monoxide, the nitrogen monoxide is not easy to be absorbed, and the nitrogen oxides are oxidized into high-valence nitrogen oxides such as nitrogen dioxide, the nitrogen oxides are absorbed by a desulfurizer at first, most of the sulfur dioxide in the flue gas is removed, meanwhile, the desulfurizer absorbs the sulfur dioxide in the flue gas to obtain desulfurization slurry rich in sulfite, then, the flue gas is subjected to high-efficiency liquid-phase oxidation to oxidize the nitrogen monoxide in the flue gas into nitrogen dioxide, part of the nitrogen dioxide is absorbed by an oxidant to form nitrate slurry, the nitrate can obtain byproducts such as fertilizers after subsequent treatment, and the chlorite is taken as the oxidant, and a specific reaction equation of the oxidation reaction is as follows:
2NO+ClO2 -→2NO2+Cl
4NO2+ClO2 -+4OH-→4NO3-+Cl-+2H2O
NO+ClO2 -→NO2+ClO
NO+ClO-→NO2+Cl
2NO2+ClO2 -+2OH-→2NO3 -+ClO-+2H2O
and finally, performing secondary absorption on the flue gas by using the desulfurized slurry after the primary desulfurization to remove nitrogen dioxide and residual sulfur dioxide in the flue gas to form sulfate slurry, wherein the sulfate slurry is subjected to subsequent treatment to obtain a byproduct such as gypsum, and the reaction equation for absorbing the nitrogen dioxide during the secondary absorption is as follows:
4SO3 2-+2NO2+→N2+4SO4 2-
the desulfurizer of the invention is ammonia water, seawater, magnesium hydroxide or limestone slurry, the pH value and liquid-gas ratio of the desulfurizer are set according to the content of sulfur dioxide in flue gas and the type of the selected desulfurizer, and as a preferred technical scheme, the desulfurizer selects calcium hydroxide or limestone slurry. The oxidant used by the oxidant storage tank is an aqueous solution of at least one of hydrogen peroxide, chlorite and hypochlorite; the chlorite can be at least one of sodium chlorite, hypochlorite can be at least one of sodium hypochlorite and calcium hypochlorite.
However, in the actual tail gas treatment process, the defects of insufficient NO oxidation and excessive using amount of the oxidant often exist, and aiming at the defects, the invention further loads an NO oxidation catalyst on the second treatment section of the waste gas treatment device, wherein the catalyst is an immobilized ionic liquid low-temperature denitration catalyst and comprises 1-60% by weight of active components and 40-99% by weight of carriers, and the active components are polyether ionic liquid containing Mg or Al ions.
The carrier is selected from MFI, ERI and MOR type molecular sieves having a strong adsorption capacity for NO, and particularly preferred are 13X and H beta molecular sieves.
The polyether ionic liquid has the following structural formula:
[R1(OCH2CH2)mCH2CH2NR2 3]+·X-
in the formula R1Is C1-6 alkyl, R2Is C2-6 hydroxyalkyl, the R is2May be the same or different from each other.
The preparation method of the NO oxidation catalyst comprises the following steps: dispersing active metal and ionic liquid in a solvent to form a solution, immersing a carrier in the solution, stirring the solution at room temperature for 18-24 hours, filtering out the immersed solution, and finally, putting the immersed carrier in a positive air drying oven for vacuum drying at 100 ℃ for 8-12 hours to remove the solvent to obtain the immobilized ionic liquid low-temperature denitration catalyst.
The active component of the catalyst is a microenvironment formed by polyether ionic liquid formed by active metal Mg and Al, so that the contact of the active component and water can be effectively prevented, and the active component is not easy to lose in the reaction process, thereby prolonging the service life of the catalyst; the ionic liquid has the characteristics of difficult volatilization, high thermal stability and the like, the ionic liquid is combined with a molecular sieve material with strong adsorption capacity to NO, the high catalytic activity of the ionic liquid is maintained, the active components are highly dispersed, the active components are uniformly distributed on the surface of a carrier, the agglomeration of the active components can be effectively prevented, the specific surface area of the catalyst is large, the catalytic activity is high, and the reaction selectivity is good.
The invention discloses a high-efficiency flue gas treatment device taking solar energy as power and a multi-section waste gas treatment method, which have the following beneficial effects:
the invention integrates the desulfurization and denitrification into one treatment tower, so that the desulfurization working section and the denitrification working section are independent and related to each other, thereby greatly simplifying the process flow, reducing the floor area of equipment and lowering the investment cost.
The sulfur dioxide in the waste gas is firstly removed before denitration oxidation, most of the sulfur dioxide is removed, and then denitration oxidation is carried out, so that the side reaction of the oxidant and the sulfur dioxide can be reduced, the consumption of the oxidant is reduced, and the operation cost is saved.
Adopt microchannel absorbing device and with the device cooperation spray plate that uses in the third treatment stage to greatly increased the area of contact of waste gas with the absorption liquid, prolonged the contact time of waste gas with the absorption liquid, be favorable to abundant desorption nitrogen dioxide, improved the denitration rate.
By additionally arranging the immobilized ionic liquid denitration catalyst with high catalytic activity in the second treatment stage, the denitration rate is greatly improved while the use amount of the oxidant is reduced.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiment or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic structural diagram of a solar-powered high-efficiency flue gas treatment device according to an embodiment of the present invention;
in the figure: 1-a treatment tower, 2-a slurry tank, 3-a first circulating pump, 4-a second circulating pump, 5-an oxidant tank, 6-a circulating tank, 7-a fresh desulfurization slurry preparation tank, 8-a solar power generation unit, 9-a dosing device, 10-a waste gas inlet, 11-a first treatment section, 12-a second treatment section, 13-a third treatment section, 14-a first liquid collecting and gas lifting device, 15-a second liquid collecting and gas lifting device, 16-a defoaming device, 17-a waste gas outlet, 61-a first circulating pipeline, 62-a second circulating pipeline, 111-a first spraying pipe, 112-a packing layer, 131-a micro-channel absorption device, 132-a spraying plate, 161-a defoaming device body, 162-an automatic flushing system and 162a spraying pipe, 163-industrial water tank.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, apparatus, article, or device that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or device.
Example 1
The embodiment provides a multi-stage exhaust gas treatment device using solar energy as power, which has high desulfurization and denitrification efficiency and low operation cost, and particularly, please refer to fig. 1.
As shown in fig. 1, the multistage exhaust gas treatment apparatus includes a treatment tower 1 and a slurry tank 2, and the slurry tank 2 is disposed at the bottom 1 of the treatment tower and communicates with the treatment tower 1.
The treatment tower 1 is sequentially divided into a first treatment section 11, a second treatment section 12 and a third treatment section 13 from bottom to top, a first liquid collecting and air lifting device 14 is arranged between the first treatment section 11 and the second treatment section 12, and a second liquid collecting and air lifting device 15 is arranged between the second treatment section 12 and the third treatment section 13.
The first treatment section 11 is provided with a waste gas inlet 10, and the first treatment section 11 is used for removing sulfur dioxide gas in waste gas. In one embodiment, the waste gas inlet 10 is arranged to form an angle of 10-30 degrees with the horizontal direction, so that the waste gas can be uniformly distributed, and the spraying liquid can be prevented from refluxing, so that the waste gas in the treatment tower 1 can have enough residence time.
The second treatment section 12 is used for oxidizing nitric oxide gas in the waste gas to convert the nitric oxide gas into nitrogen dioxide, and the third treatment section 13 is used for removing nitrogen oxide in the waste gas and discharging the treated gas out of the treatment tower.
The first treatment section 11 and the third treatment section 13 are communicated with the slurry tank 2 through a first circulating pump 3, the second treatment section 12 is communicated with an oxidant storage tank 5 through a second circulating pump 4, the oxidant storage tank 5 and the second treatment section 12 form a closed circulation, and a catalyst is additionally arranged on the second treatment section. The closed cycle can improve the utilization rate of the oxidant and reduce the cost.
The third treatment section 13 is also communicated with a circulation tank 6 through a first circulation pipeline 61, the circulation tank 6 is used for collecting the absorption liquid in the third treatment section 13, a dosing device 9 is arranged on the circulation tank 6, and the circulation tank 6 is communicated with the slurry tank 2 through a second circulation pipeline 62.
The device further comprises a solar power generation unit 8, wherein the solar power generation unit 8 is electrically connected with the first circulating pump 3 and the second circulating pump 4 and used for providing power electricity for the first circulating pump 3 and the second circulating pump 4. Of course, it will be appreciated that the solar power unit 8 may also provide power to other devices that require power to be consumed.
In one embodiment, a first spray absorption device is disposed in the first treatment stage 11, a second spray absorption device is disposed in the second treatment stage 12, and a third spray absorption device is disposed in the third treatment stage 13. The liquid-phase absorption liquid is atomized by the corresponding spraying absorption device, and the absorption efficiency is increased.
The third spray absorption device comprises a micro-channel absorption device 131 arranged at the upper part of the second liquid collecting and gas lifting device 15, a hollow spray plate 132 is arranged on the micro-channel absorption device 131, the spray plate 132 is communicated with the outlet of the first circulating pump 3 through a first spray pipeline 31, the first circulating pump 3 pumps the slurry in the slurry tank 2 to the spray plate 132 through the first spray pipeline 31, and the slurry is sprayed into the micro-channel absorption device 131 through the spray plate 132. The arrangement of the micro-channel absorption device 131 greatly increases the contact area and the contact time of the absorption liquid and the waste gas, thereby effectively promoting mass transfer and being beneficial to improving the efficiency of desulfurization and denitrification.
The first spraying absorption device comprises a first spraying pipe 111 and a packing layer 112, the first spraying pipe 111 is arranged on the upper portion of the packing layer 112, the first spraying pipe 111 is communicated with an outlet of the first circulating pump 3 through a second spraying pipeline 32, the first circulating pump 3 pumps the slurry in the slurry tank 2 to the first spraying pipe 111 through the second spraying pipeline 32, and the slurry is sprayed into the first treatment section 11 through the first spraying pipe 11.
In one embodiment, the treatment tower 1 is provided with a demister near the exhaust gas outlet 17, the demister comprising a demister body 161 and an automatic flushing system comprising showers 162a disposed at upper and lower portions of the demister body 161 and an industrial water tank 163 communicating with the showers 162 a. The arrangement of the defoaming device ensures the normal operation of the treatment tower 1 and ensures that the process water is available in case of emergency.
In one embodiment, the slurry tank 2 is communicated with the inlet of the first circulation pump 3 through a first suction pipeline 33, a first branch 34 is branched from the first suction pipeline 33, one end of the first branch 34 is connected with the first suction pipeline 33, the other end of the first branch 34 is connected with the circulation tank 6, a second branch 35 is branched from the first branch 34, and the second branch 35 is used for being communicated with the fresh desulfurization slurry preparation tank 7.
In the embodiment, the desulfurization and denitrification are integrated in one treatment tower, so that the desulfurization working section and the denitrification working section are independent and related to each other, the process flow is greatly simplified, the floor area of equipment is reduced, and the investment cost is reduced.
Adopt microchannel absorbing device and with the device cooperation spray plate that uses in the third treatment stage to greatly increased the area of contact of waste gas with the absorption liquid, prolonged the contact time of waste gas with the absorption liquid, be favorable to abundant desorption nitrogen dioxide, improved the denitration rate.
Example 2
The embodiment provides a multi-stage waste gas treatment method, in particular to a flue gas treatment method, which utilizes any one of the multi-stage waste gas treatment devices using solar energy as power in the embodiment, and specifically comprises the following steps:
1) the waste gas to be treated enters a first treatment section, the waste gas to be treated is contacted with a desulfurizing agent in the first treatment section, and the desulfurizing agent absorbs partial sulfur dioxide in the waste gas to be treated to obtain desulfurization slurry;
2) the waste gas treated by the first treatment section enters a second treatment section for liquid phase oxidation and partial absorption, so that nitric oxide in the waste gas is oxidized into nitrogen dioxide;
3) and (3) the waste gas treated by the second treatment section enters a third treatment section, and the oxidized waste gas is contacted with the desulfurization slurry in the step 1) in the third treatment section, and the desulfurization slurry absorbs nitrogen dioxide and the rest sulfur dioxide in the waste gas.
Specifically, the flue gas after dust removal is conveyed to the treatment tower 1 through the induced draft fan, and a desulfurization link is carried out in the first treatment section 11 of the treatment tower 1, SO that the desulfurization slurry and SO2And the fine dust generates sufficient absorption and mass transfer, and after the oxidation link is completed through the second treatment section 12, the fine dust is conveyed to the denitration link of the third treatment section 13 by using a liquid collection and gas lifting device, and is in reverse contact with the denitration liquid from top to bottom in the micro-channel absorption device, so that the nitrogen oxides in the flue gas are sufficiently eliminated, and finally, the demisting device is used for removing water and mist in the flue gas and discharging the water and mist from a waste gas outlet 17 of the treatment tower 1. In the second treatment stage, the oxidizing agent sprayed from the oxidizing agent tank 5 oxidizes the nitrogen monoxide in the flue gas to nitrogen dioxide.
Flue gas from a boiler flue contains a large amount of sulfur dioxide and nitrogen oxides, the nitrogen oxides mainly comprise nitrogen monoxide, the nitrogen monoxide is not easy to be absorbed, and the nitrogen oxides are oxidized into high-valence nitrogen oxides such as nitrogen dioxide, the nitrogen oxides are absorbed by a desulfurizer at first, most of the sulfur dioxide in the flue gas is removed, meanwhile, the desulfurizer absorbs the sulfur dioxide in the flue gas to obtain desulfurization slurry rich in sulfite, then, the flue gas is subjected to high-efficiency liquid-phase oxidation to oxidize the nitrogen monoxide in the flue gas into nitrogen dioxide, part of the nitrogen dioxide is absorbed by an oxidant to form nitrate slurry, the nitrate can obtain byproducts such as fertilizers after subsequent treatment, and the chlorite is taken as the oxidant, and a specific reaction equation of the oxidation reaction is as follows:
2NO+ClO2 -→2NO2+Cl
4NO2+ClO2 -+4OH-→4NO3-+Cl-+2H2O
NO+ClO2 -→NO2+ClO
NO+ClO-→NO2+Cl
2NO2+ClO2 -+2OH-→2NO3 -+ClO-+2H2O
and finally, performing secondary absorption on the flue gas by using the desulfurized slurry after the primary desulfurization to remove nitrogen dioxide and residual sulfur dioxide in the flue gas to form sulfate slurry, wherein the sulfate slurry is subjected to subsequent treatment to obtain a byproduct such as gypsum, and the reaction equation for absorbing the nitrogen dioxide during the secondary absorption is as follows:
4SO3 2-+2NO2+→N2+4SO4 2-
the desulfurizer described in this embodiment is ammonia water, seawater, magnesium hydroxide or limestone slurry, and the pH value and liquid-gas ratio of the desulfurizer are set according to the content of sulfur dioxide in flue gas and the type of the selected desulfurizer. The oxidant used by the oxidant storage tank is an aqueous solution of at least one of hydrogen peroxide, chlorite and hypochlorite; the chlorite can be at least one of sodium chlorite, hypochlorite can be at least one of sodium hypochlorite and calcium hypochlorite.
However, in the actual tail gas treatment process, the defects of insufficient NO oxidation and excessive using amount of the oxidant often exist, and aiming at the defects, the invention further loads an NO oxidation catalyst on the second treatment section of the waste gas treatment device, wherein the catalyst is an immobilized ionic liquid low-temperature denitration catalyst and comprises 1-60% by weight of active components and 40-99% by weight of carriers, and the active components are polyether ionic liquid containing Mg or Al ions.
The carrier is selected from MFI, ERI and MOR type molecular sieves having a strong adsorption capacity for NO, and particularly preferred are 13X and H beta molecular sieves.
The polyether ionic liquid has the following structural formula:
[R1(OCH2CH2)mCH2CH2NR2 3]+·X-
in the formula R1Is C1-6 alkyl, R2Is C2-6 hydroxyalkyl, the R is2May be the same or different from each other.
The preparation method of the NO oxidation catalyst comprises the following steps: dispersing active metal and ionic liquid in a solvent to form a solution, immersing a carrier in the solution, stirring the solution at room temperature for 18-24 hours, filtering out the immersed solution, and finally, putting the immersed carrier in a positive air drying oven for vacuum drying at 100 ℃ for 8-12 hours to remove the solvent to obtain the immobilized ionic liquid low-temperature denitration catalyst.
The active component of the catalyst is a microenvironment formed by polyether ionic liquid formed by active metal Mg and Al, so that the contact of the active component and water can be effectively prevented, and the active component is not easy to lose in the reaction process, thereby prolonging the service life of the catalyst; the ionic liquid has the characteristics of difficult volatilization, high thermal stability and the like, the ionic liquid is combined with a molecular sieve material with strong adsorption capacity to NO, the high catalytic activity of the ionic liquid is maintained, the active components are highly dispersed, the active components are uniformly distributed on the surface of a carrier, the agglomeration of the active components can be effectively prevented, the specific surface area of the catalyst is large, the catalytic activity is high, and the reaction selectivity is good.
In the desulfurization link, sulfite also appears in the slurry, and the product returns to the slurry tank 2 at the bottom of the treatment tower 1 along with the slurry, and is recirculated to the desulfurization link through the second spraying pipeline 32 under the action of the first circulating pump 3 for desulfurization, while the rest of the slurry tank 2 is conveyed to the denitration link through the first spraying pipeline 31 under the action of the first circulating pump 3 for denitration. The absorption liquid generated in the denitration step enters the circulation tank 6 through the first circulation pipeline 61, and a proper amount of medicine is added into the circulation tank 6 through the medicine adding device 9 to promote the removal of nitrogen oxides. The bottom of the circulation tank 6 communicates with the slurry tank 2 through the second circulation line 62, so that the slurry in the circulation tank 6 can be transferred into the slurry tank 2 to continue the circulation. The circulation tank 6 can be timely replenished with fresh desulfurization slurry through the first branch 34 and the second branch 35, and the fresh desulfurization slurry enters the slurry tank 2 through the second circulation line 62. In the circulation tank 6, the slurry and the drug and the newly added new slurry can be sufficiently mixed.
Example 3
Preparing polyether ionic liquid: adding monochloropolyethylene glycol (M is 500) and triethanolamine into a reactor according to a molar ratio of 1:1.1, using toluene as a solvent, stirring and refluxing for 96 hours under a nitrogen atmosphere, stopping the reaction, respectively washing with acetone, ethyl acetate and diethyl ether, washing for several times, and then performing vacuum drying to obtain PEG-TEA ionic liquid;
the preparation of the immobilized ionic liquid low-temperature denitration catalyst comprises the following steps: adding equimolar amount of AlCl into the PEG-TEA ionic liquid under the protection of nitrogen3Stirring for reacting for 6h, adding a certain amount of ethanol, adding a certain amount of 13X molecular sieve after the ionic liquid is completely dissolved, stirring at room temperature overnight, filtering, placing in a vacuum drying oven for vacuum drying at 150 ℃ for 12h, crushing the obtained solid, and sieving with a 30-60-mesh sieve to obtain the immobilized ionic liquid catalyst particles.
Example 4
Preparing polyether ionic liquid: adding monochloropolyethylene glycol (M is 500) and triethanolamine into a reactor according to a molar ratio of 1:1.1, using toluene as a solvent, stirring and refluxing for 96 hours under a nitrogen atmosphere, stopping the reaction, respectively washing with acetone, ethyl acetate and diethyl ether, washing for several times, and then performing vacuum drying to obtain PEG-TEA ionic liquid;
preparation of immobilized ionic liquid low-temperature denitration catalystPreparing: adding equimolar MgCl into the PEG-TEA ionic liquid under the protection of nitrogen2Stirring for reaction for 6H, adding a certain amount of ethanol, adding an H β molecular sieve in a weight ratio of 1:2 after the ionic liquid is completely dissolved, stirring overnight at room temperature, filtering, placing in a vacuum drying oven for vacuum drying at 150 ℃ for 12H, and sieving with a 30-60-mesh sieve to obtain the immobilized ionic liquid catalyst particles.
Example 5
According to the apparatus shown in FIG. 1, 3kg of the supported ionic liquid catalyst prepared in example 3 was loaded at 8m in the second treatment stage3And simulating the flue gas desulfurization and denitrification process on an experimental simulation device of the/h scale. Flue gas volume 8m3The smoke components are as follows: o is28% of SO23000ppm, NO 4 × 104ppm, the balance of nitrogen, the flue gas temperature of 100 ℃ and the pressure of 1 atmosphere. Using 10% sodium chlorite solution as oxidant and 17% ammonia water as desulfurizing agent, and the liquid-gas ratio of liquid-phase oxidation is 2L/m3The waste gas treatment process is utilized to carry out desulfurization and denitrification. Through detection, the overall desulfurization efficiency is 99.6%, and the denitration efficiency can reach 98.5%.
Example 6
3kg of the supported ionic liquid catalyst prepared in example 4 was loaded in the second treatment stage by the apparatus shown in FIG. 1, and the desulfurization and denitrification were carried out by the exhaust gas treatment process of the present invention in the same manner as in example 5. Through detection, the overall desulfurization efficiency is 99.3%, and the denitration efficiency can reach 98.0%.
Comparative example 1
In the apparatus shown in FIG. 1, 3kg of 13X molecular sieve was charged in the second treatment stage, and the same operation as in example 5 was carried out to remove sulfur and nitrogen by the exhaust gas treatment process of the present invention. Through detection, the overall desulfurization efficiency is 95%, and the denitration efficiency can reach 70%.
Comparative example 2
In the apparatus shown in FIG. 1, 3kg of Hbeta molecular sieve was loaded in the second treatment stage, and the desulfurization and denitrification were carried out by the exhaust gas treatment process of the present invention in the same manner as in example 5. Through detection, the total desulfurization efficiency is 97%, and the denitration efficiency can reach 76%.
Comparative example 3
In the apparatus shown in FIG. 1, the second treatment stage was carried out without any catalyst, and the same operation as in example 5 was carried out to remove sulfur and nitrogen by the exhaust gas treatment process of the present invention. Through detection, the overall desulfurization efficiency is 94%, and the denitration efficiency can reach 76%.
The invention integrates the desulfurization and denitrification into one treatment tower, so that the desulfurization working section and the denitrification working section are independent and related to each other, thereby greatly simplifying the process flow, reducing the floor area of equipment and lowering the investment cost.
The sulfur dioxide in the waste gas is firstly removed before denitration oxidation, most of the sulfur dioxide is removed, and then denitration oxidation is carried out, so that the side reaction of the oxidant and the sulfur dioxide can be reduced, the consumption of the oxidant is reduced, and the operation cost is saved.
Adopt microchannel absorbing device and with the device cooperation spray plate that uses in the third treatment stage to greatly increased the area of contact of waste gas with the absorption liquid, prolonged the contact time of waste gas with the absorption liquid, be favorable to abundant desorption nitrogen dioxide, improved the denitration rate.
Compared with the situation that only the molecular sieve is loaded and no catalyst is loaded, the solid-supported ionic liquid denitration catalyst with high catalytic activity provided by the invention is additionally arranged in the second treatment section, under the same operation condition, the denitration rate is greatly improved while the use amount of the oxidant is reduced.
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (1)
1. A high-efficiency flue gas treatment device taking solar energy as power comprises a treatment tower and a slurry tank, wherein the slurry tank is arranged at the bottom of the treatment tower and is communicated with the treatment tower, and the treatment tower is sequentially divided into a first treatment section, a second treatment section and a third treatment section from bottom to top, a first liquid collecting and gas lifting device is arranged between the first treatment section and the second treatment section, a second liquid collecting and gas lifting device is arranged between the second treatment section and the third treatment section, the first treatment section is provided with a waste gas inlet, the first treatment section is used for removing sulfur dioxide gas in waste gas, the second treatment section is used for oxidizing nitric oxide gas in the waste gas to convert the nitric oxide gas into nitrogen dioxide, the third treatment section is used for removing nitrogen oxide in the waste gas and discharging the treated gas out of the treatment tower,
the first treatment section and the third treatment section are communicated with the slurry tank through a first circulating pump, the second treatment section is communicated with an oxidant storage tank through a second circulating pump, the oxidant storage tank and the second treatment section form a closed circulation, a catalyst is additionally arranged on the second treatment section, the device further comprises a solar power generation unit, and the solar power generation unit is electrically connected with the first circulating pump and the second circulating pump;
the second treatment section of the waste gas treatment device is loaded with a NO oxidation catalyst, the catalyst is a solid-supported ionic liquid low-temperature denitration catalyst and comprises 1-60% of active components and 40-99% of carriers by weight, and the active components are polyether ionic liquid containing Mg or Al ions;
the carrier is selected from 13X and H beta molecular sieves with strong adsorption capacity to NO;
the polyether ionic liquid has the following structural formula:
[R1(OCH2CH2)mCH2CH2NR2 3]+·X-
in the formula R1Is C1-6 alkyl, R2Is C2-6 hydroxyalkyl, the R is2The same or different from each other;
the preparation method of the NO oxidation catalyst comprises the following steps: dispersing active metal and ionic liquid in a solvent to form a solution, immersing a carrier in the solution, stirring the solution at room temperature for 18-24 hours, filtering out the immersed solution, and then placing the immersed carrier in a vacuum drying oven for vacuum drying at 100 ℃ for 8-12 hours to remove the solvent to obtain the immobilized ionic liquid low-temperature denitration catalyst;
a first spraying absorption device is arranged in the first treatment section, a second spraying absorption device is arranged in the second treatment section, a third spraying absorption device is arranged in the third treatment section, the third spraying absorption device comprises a micro-channel absorption device arranged on the upper part of the second liquid collecting and gas lifting device, a hollow spraying plate is arranged on the micro-channel absorption device, the spraying plate is communicated with an outlet of the first circulating pump through a first spraying pipeline, the first circulating pump pumps the slurry in the slurry tank to the spraying plate through the first spraying pipeline, and the slurry is sprayed into the micro-channel absorption device through the spraying plate; the third treatment section is also communicated with a circulating tank through a first circulating pipeline, the circulating tank is used for collecting absorption liquid in the third treatment section, a dosing device is arranged on the circulating tank, and the circulating tank is communicated with the slurry tank through a second circulating pipeline;
the first spraying absorption device comprises a first spraying pipe and a packing layer, the first spraying pipe is arranged at the upper part of the packing layer, the first spraying pipe is communicated with an outlet of the first circulating pump through a second spraying pipeline, the first circulating pump pumps the slurry in the slurry tank to the first spraying pipe through the second spraying pipeline, and the slurry is sprayed into the first treatment section through the first spraying pipe;
the treatment tower is provided with a demisting device near the exhaust gas outlet, the demisting device comprises a demister body and an automatic flushing system, and the automatic flushing system comprises spray pipes arranged at the upper part and the lower part of the demister body and an industrial water tank communicated with the spray pipes;
the slurry tank is communicated with an inlet of the first circulating pump through a first suction pipeline, a first branch is divided from the first suction pipeline, one end of the first branch is connected with the first suction pipeline, the other end of the first branch is connected with the circulating tank, a second branch is divided from the first branch and is used for being communicated with a fresh desulfurization slurry preparation tank.
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| CN112439318A (en) * | 2019-09-05 | 2021-03-05 | 大连海事大学 | High-efficient SOx/NOx control integration system of low temperature tail gas |
| CN110585872B (en) * | 2019-10-11 | 2021-08-10 | 安徽天顺环保设备股份有限公司 | Dust removal SOx/NOx control integration tower |
| CN111495139A (en) * | 2020-04-27 | 2020-08-07 | 安徽顺达环保科技股份有限公司 | Wet-type desulfurization and denitrification device and process for high-sulfur-concentration flue gas |
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| WO2015158849A1 (en) * | 2014-04-16 | 2015-10-22 | Danmarks Tekniske Universitet | Combined oxidation and absorption of nox by an ionic liquid tandem process |
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| CN101612511A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of absorption H 2The micro-channel absorber of S |
| CN102580496A (en) * | 2012-03-14 | 2012-07-18 | 杭州天蓝环保设备有限公司 | Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device |
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